CN1300880C - Supporting electrolyte for cell and method for production thereof, and cell - Google Patents

Supporting electrolyte for cell and method for production thereof, and cell Download PDF

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Publication number
CN1300880C
CN1300880C CNB038171864A CN03817186A CN1300880C CN 1300880 C CN1300880 C CN 1300880C CN B038171864 A CNB038171864 A CN B038171864A CN 03817186 A CN03817186 A CN 03817186A CN 1300880 C CN1300880 C CN 1300880C
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general formula
phosphazene derivative
electrolyte
substituting group
battery
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CN1669165A (en
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大月正珠
江口真一
菅野裕士
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Bridgestone Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/062—Organo-phosphoranes without P-C bonds
    • C07F9/065—Phosphoranes containing the structure P=N-
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
    • C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A support salt for a cell comprising a compound represented by the following formula (I) or (II): (in the formulae (I) and (II), A<1> is independently NRLi or F, and at least one of A<1>s is NRLi, and R is a monovalent substituent) has an effect of suppressing combustion, and a non-aqueous electrolyte cell and a polymer cell using such a support salt considerably reduce the risk of ignition-fire and are high in the safety.

Description

Supporting electrolyte for cell and its preparation method and battery
Technical field
The present invention relates to the battery with nonaqueous electrolyte and the polymer battery of supporting electrolyte for cell and preparation method thereof and this supporting electrolyte of use, particularly a kind of supporting electrolyte for cell with burning inhibition effect.
Background technology
Recently, along with the fast development of electronic technology, be starved of size is little, in light weight, life cycle is long and energy density is high battery power supply as compact electronic device.The battery with nonaqueous electrolyte that known employing lithium is made negative electrode active material is a kind of battery with high-energy-density because in metal the electrode potential of lithium be minimum and the capacitance of per unit volume big.The such battery of many kinds has all passed through positive research, no matter primary cell or secondary cell, and wherein a part is used and is gone on the market.For example, the nonaqueous electrolytic solution primary cell is as the power supply of camera, electronic watch and various storage backup equipment, and the non-aqueous solution electrolysis liquid secondary battery is as the driving power of subnotebook PC, mobile phone etc.
In these battery with nonaqueous electrolyte, because as the lithium of negative electrode active material and compound such as the vigorous reactions such as water, alcohol with active proton, so the electrolyte in these batteries is limited to proton-inert organic solvent as based on the organic solvent of ester etc.
Up to now, in nonaqueous electrolytic solution secondary battery, use dividing plate to prevent that positive pole from contacting with negative pole.Employing porous membrane etc. is made dividing plate and is stoped the nonionic in the electrolyte to move.But film does not have the ability that keeps electrolyte, thereby is adopting film to do to have in the battery of dividing plate the danger of leak of liquid.
On the other hand, developing recently and adopt polymer to make electrolytical polymer battery, is a kind of battery of not worrying leak of liquid.Especially, study polymer battery recently more and more, because can form film, and except not worrying leak of liquid, its assembling on electronic installation is good, and can effectively utilize the space.As the electrolyte that uses in polymer battery, known has by carry true polymers (truepolymer) electrolyte and the gel electrolyte by forming with the organic solvent swollen polymer that lithium salts forms on polymer.But the true polymers electrolyte has a problem, and promptly ionic conductivity is more much lower than gel electrolyte.
And on the other hand, in the polymer battery that adopts gel electrolyte, the same with above-mentioned nonaqueous electrolytic solution secondary battery, make negative material owing to use lithium metal or lithium alloy, negative pole and compound such as vigorous reactions such as water, alcohol with active proton, thereby the same with above-mentioned battery with nonaqueous electrolyte, the organic solvent that adopts in the gel electrolyte is limited to proton-inert organic solvent as based on organic solvent of ester etc.
Usually, in the electrolyte of the nonaqueous electrolytic solution of battery with nonaqueous electrolyte or polymer battery, use lithium salts such as LiClO 4, LiCF 3SO 3, LiAsF 6, LiC 4F 9SO 3, Li (CF 3SO 2) 2N, Li (C 2F 5SO 2) 2N, LiBF 4, LiPF 6Deng as supporting electrolyte, so that provide enough conductibility for electrolyte and solid electrolyte.
Summary of the invention
As mentioned above, battery with nonaqueous electrolyte has the high advantage of energy density, and polymer battery has the advantage of not worrying electrolyte leakage, the assembling on electronic installation is good and can effectively utilizes the space, but the negative material in these battery with nonaqueous electrolyte and polymer battery is lithium metal or lithium alloy, water there is very high activity, thereby there is a problem, promptly when cell sealing not exclusively or water infiltrate its medium situation when occurring, negative material and water reaction generate hydrogen or cause igniting etc., and therefore danger uprise.Simultaneously, because the fusing point low (about 170 ℃) of lithium metal also has a problem,, can cause breakneck state such as battery and produce abnormal heat, battery fusing etc. if promptly electric current is mobile rapidly greatly in situations such as short circuit.In addition, also have a problem, be accompanied by above-mentioned battery with nonaqueous electrolyte and polymer battery and produce heat, can be evaporated and decompose based on the nonaqueous electrolytic solution of organic solvent and the organic solvent in the polymer battery electrolyte, produce gas, perhaps cause battery explosion-igniting by the gas that produces.
In addition, also have a problem, oxygen containing supporting electrolyte can discharge oxygen in heating-burning in above-mentioned conventional supporting electrolyte, promotes the burning of battery.On the other hand, oxygen-free supporting electrolyte such as LiBF 4, LiPF 6Deng not promoting burning, poor but it suppresses effect of combustion.In the battery with nonaqueous electrolyte and polymer battery that adopt above-mentioned supporting electrolyte, the danger of igniting etc. are still higher.
Therefore, an object of the present invention is to provide a kind of supporting electrolyte that is used for battery with nonaqueous electrolyte and polymer battery that burning suppresses effect that has.Simultaneously, another object of the present invention provides a kind of battery with nonaqueous electrolyte that adopts the safety of this supporting electrolyte.In addition, a further object of the invention provides a kind of safe polymer battery, and it has reduced the danger of ignition by adopting this supporting electrolyte.
To achieve these goals, the inventor has carried out various researchs, and newly developed to have gone out with phosphazene derivative (phosphazene) be the compound that contains lithium in basic framework and its molecule, use this compound to make supporting electrolyte, the battery with nonaqueous electrolyte and the polymer battery of the safety of low ignition danger of combustion can be provided, and this is because this compound has the inhibition effect of combustion.
That is to say that the present invention is as follows.
1. supporting electrolyte for cell, it comprises by the following general formula (I) or (II) compound of expression:
(at general formula (I) with (II), A 1Be NRLi or F independently, and at least one A 1Be NRLi, R is the monovalence substituting group).
2. according to the 1st supporting electrolyte for cell, its formula of (I) and (II) in R be phenyl.
3. method for preparing supporting electrolyte for cell, it comprises the following steps:
(i) with the phosphazene derivative of following general formula (III) expression and the primary amine reaction of following general formula (IV) expression, prepare the phosphazene derivative of following general formula (V) expression; With
(ii) in the phosphazene derivative of general formula (V), add pure lithium salts, the compound of preparation following formula (I) expression:
Figure C0381718600111
(A wherein 2Be F or Cl)
R-NH 2 .....(IV)
(wherein R is the monovalence substituting group)
Figure C0381718600112
(A wherein 3Be NHR or F independently, and at least one A 3Be NHR, R is the monovalence substituting group)
(A wherein 1Be NRLi or F independently, and at least one A 1Be NRLi, R is the monovalence substituting group).
4. according to the 3rd the method for preparing supporting electrolyte for cell, the primary amine of its formula of (IV) is an aniline.
5. method for preparing supporting electrolyte for cell, it comprises the following steps:
(i) with the phosphazene derivative of following general formula (VI) expression and the primary amine reaction of following general formula (IV) expression, the phosphazene derivative of logical following formula (VII) expression of preparation; With
(ii) in the phosphazene derivative of general formula (VII), add pure lithium salts, the compound of preparation following formula (II) expression:
Figure C0381718600121
(A wherein 2Be F or Cl)
R-NH 2 ......(IV)
(wherein R is the monovalence substituting group)
Figure C0381718600122
(A wherein 3Be NHR or F independently, and at least one A 3Be NHR, R is the monovalence substituting group)
(A wherein 1Be NRLi or F independently, and at least one A 1Be NRLi, R is the monovalence substituting group).
6. according to the 5th the method for preparing supporting electrolyte for cell, the primary amine of its formula of (IV) is an aniline.
7. a battery with nonaqueous electrolyte comprises positive pole, negative pole and nonaqueous electrolytic solution, and wherein nonaqueous electrolytic solution comprises the supporting electrolyte described in proton-inert organic solvent and the 1st.
8. according to the 7th battery with nonaqueous electrolyte, wherein in proton-inert organic solvent, add the isomers of phosphazene derivative or phosphazene derivative.
9. according to the 8th battery with nonaqueous electrolyte, wherein the viscosity of phosphazene derivative under 25 ℃ is no more than 300mPas (300cP), and represents by following general formula (VIII) or (IX):
Figure C0381718600124
(R wherein 1, R 2And R 3Be monovalence substituting group or halogen independently, X 1For comprising the substituting group of at least a element that is selected from carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulphur, selenium, tellurium and polonium, Y 1, Y 2And Y 3Be divalent linker, diad or singly-bound independently) (NPR 4 2) n... .. (IX)
(R wherein 4Be monovalence substituting group or halogen independently, n is 3-15).
10. according to the 9th battery with nonaqueous electrolyte, the phosphazene derivative of its formula of (IX) is represented by following general formula (X):
(NPF 2) n ......(X)
(wherein n is 3-13).
11. according to the 9th battery with nonaqueous electrolyte, the phosphazene derivative of its formula of (IX) is represented by following general formula (XI):
(NPR 5 2) n .....(XI)
(R wherein 5Be monovalence substituting group or fluorine independently, and all R 5In at least one be fluorine-containing monovalence substituting group or fluorine, n is 3-8, but not all R 5All be fluorine).
12. according to the 8th battery with nonaqueous electrolyte, wherein phosphazene derivative is solid down at 25 ℃, and is represented by following general formula (XII):
(NPR 6 2) n .....(XII)
(R wherein 6Be monovalence substituting group or halogen independently, n is 3-6).
13. according to the 8th battery with nonaqueous electrolyte, wherein the isomers of phosphazene derivative is represented by following general formula (XIII), and is the isomers of the phosphazene derivative of following general formula (XIV) expression:
Figure C0381718600131
(at general formula (XIII) with (XIV), R 7, R 8And R 9Be monovalence substituting group or halogen independently, X 2For comprising the substituting group of at least a element that is selected from carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulphur, selenium, tellurium and polonium, Y 7And Y 8Be divalent linker, diad or singly-bound independently).
14. a polymer battery comprises positive pole, negative pole, comprises the electrolyte and the polymer of supporting electrolyte described in the 1st.
15. according to the 14th polymer battery, wherein polymer is at least a in poly(ethylene oxide), polyacrylate and the PPOX.
16. according to the 14th or 15 polymer battery, wherein the weight average molecular weight of polymer is not less than 10000.
17. according to the 16th polymer battery, wherein the weight average molecular weight of polymer is not less than 5000000.
18. according to each polymer battery among the 14-17, wherein the total amount of relative polymer of the amount of polymer and supporting electrolyte is 80～95 quality %.
19. according to each polymer battery among the 14-18, wherein electrolyte further contains the isomers of phosphazene derivative and/or phosphazene derivative.
20. according to the 19th polymer battery, wherein the viscosity of phosphazene derivative under 25 ℃ is no more than 300mPas (300cP), and represents by following general formula (VIII) or (IX):
(R wherein 1, R 2And R 3Be monovalence substituting group or halogen independently, X 1For comprising the substituting group of at least a element that is selected from carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulphur, selenium, tellurium and polonium, Y 1, Y 2And Y 3Be divalent linker, diad or singly-bound independently)
(NPR 4 2) n ......(IX)
(R wherein 4Be monovalence substituting group or halogen independently, n is 3-15).
21. according to the 20th polymer battery, the phosphazene derivative of its formula of (IX) is represented by following general formula (X):
(NPF 2) n .....(X)
(wherein n is 3-13).
22. according to the 20th polymer battery, the phosphazene derivative of its formula of (IX) is represented by following general formula (XI):
(NPR 5 2) n .....(XI)
(R wherein 5Be monovalence substituting group or fluorine independently, and all R 5In at least one be fluorine-containing monovalence substituting group or fluorine, n is 3-8, but not all R 5All be fluorine).
23. according to the 19th polymer battery, wherein phosphazene derivative is solid down at 25 ℃, and is represented by following general formula (XII):
(NPR 6 2) n .....(XII)
(R wherein 6Be monovalence substituting group or halogen independently, n is 3-6).
24. according to the 19th polymer battery, wherein the isomers of phosphazene derivative is represented by following general formula (XIII), and is the isomers of the phosphazene derivative of following general formula (XIV) expression:
Figure C0381718600151
(at general formula (XIII) with (XIV), R 7, R 8And R 9Be monovalence substituting group or halogen independently, X 2For comprising the substituting group of at least a element that is selected from carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulphur, selenium, tellurium and polonium, Y 7And Y 8Be divalent linker, diad or singly-bound independently).
25. according to each polymer battery among the 19-24, wherein the total content of phosphazene derivative and phosphazene derivative isomers is at least 0.5 quality % in the electrolyte.
26. according to the 25th polymer battery, wherein the total content of phosphazene derivative and phosphazene derivative isomers is at least 2.5 quality % in the electrolyte.
Preferred forms of the present invention
To describe the present invention in detail below.
＜supporting electrolyte for cell 〉
Supporting electrolyte for cell according to the present invention comprises following general formula (I) or the compound of (II) representing:
(at general formula (I) with (II), A 1Be NRLi or F independently, and at least one A 1Be NRLi, R is the monovalence substituting group).
As the monovalence substituting group among general formula (I) and the R (II), that can mention has alkyl, an aryl etc.Wherein, consider that preferred phenyl especially contains the phenyl of electron withdraw group, perhaps methyl from reactive angle.
General formula (I) or (II) comprise lithium in the compound molecule of expression and is dissolved in the back with in the proton-inert organic solvent of mentioning, discharge lithium ion, so it can improve electrolytical conductibility as the ion source of lithium ion.Simultaneously, above-claimed cpd is basic framework with the phosphazene derivative, thereby it has the effect that suppresses burning.
At general formula (I) or (II), than not fluorine-containing supporting electrolyte, all A wherein 1In at least one is that the supporting electrolyte of F is suppressing better effects if aspect the combustion.And along with the increase of fluorine-containing quantity in the supporting electrolyte, the effect that suppresses burning increases.
The preparation method of＜supporting electrolyte for cell 〉
Can prepare supporting electrolyte for cell of the present invention by following method.At first, the first step is with the primary amine reaction of following general formula (III) or phosphazene derivative of (VI) representing and following general formula (IV) expression, the phosphazene derivative for preparing following general formula (V) or (VII) represent.
Figure C0381718600171
(at general formula (III) with (VI), A 2Be F or Cl)
R-NH 2 .....(IV)
(wherein R is the monovalence substituting group)
Figure C0381718600172
(at general formula (V) with (VII), A 3Be NHR or F independently, and at least one A 3Be NHR, R is the monovalence substituting group).
As the monovalence substituting group among general formula (IV), (V) and the R (VII), can mention for identical those described in general formula (I) and the monovalence substituting group (II).Similarly, consider preferred phenyl or methyl from reactive angle.
At general formula (III) with (VI), as all A 2During for F, can change the number of the amino that will introduce by the amount that changes used general formula (IV) primary amine.The amount of used general formula (IV) primary amine doubly is advisable with the 1.5-2 that the amino that will introduce replaces number.For example, in an amino situation about replacing, per 1 mole of general formula (III) or phosphazene derivative (VI) use 1.5-2 mole primary amine, are the 3.0-4.0 mole in the situation of two replacements, perhaps are the 4.5-6.0 mole in the situation of three replacements.In the first step, can be by adding alkali-metal carbonate such as accelerated reactions such as potash, sodium carbonate.The consumption of alkali carbonate be preferably used amine molal quantity 1.2-3 doubly.The effect of alkali carbonate is HF or the HCl that neutralization reaction produces, and prevents the system acidifying.If system becomes acidity, then can reduce productive rate and cause bad influence such as side reaction increase etc.
By all A wherein 2For the general formula (III) of Cl and (VI) phosphazene derivative and fluorization agent reaction, obtain wherein all A 2Be the general formula (III) of F and (VI) phosphazene derivative.As fluorization agent, that can mention has alkali metal fluoride such as NaF, a KF etc., and wherein NaF is because cheap thereby be preferred, but uses KF no problem at aspect of performance.The consumption of fluorization agent is the phosphazene derivative of 7 moles/per 1 mole of general formula (III), the phosphazene derivative of 6 moles/per 1 mole of general formula (VI), but consumption can increase a little or reduce according to reaction condition.When equivalent is excessive, reduce productive rate easily, and equivalent is when too small, has and partially fluorinatedly do not carry out.The inventor has carried out various researchs, finds that the consumption of preferred as alkali fluoride is counted the 6.5-8 mole with the phosphazene derivative of general formula (III), perhaps counts the 5.4-6.8 mole with the phosphazene derivative of general formula (VI).
Consider wherein all A 2For the boiling point of general formula (III) phosphazene derivative of F is 51 ℃ and all A wherein 2For the boiling point of general formula (VI) phosphazene derivative of F is that 97 ℃ and fluorination reaction are exothermic reactions, preferably in acetonitrile, carry out fluorination reaction, in the situation of the phosphazene derivative of general formula (III), reflux down simultaneously, or in the situation of the phosphazene derivative of general formula (VI), reflux down at about 90 ℃ at 60-80 ℃.The consumption of acetonitrile is per 1 mole of general formula of 100-1000mL/ (III) or phosphazene derivative (VI).But this quantity of solvent only is an explanation, because this reaction is solid-liquid reaction, therefore as long as can not cause precipitation by stirring, its consumption is just enough.By near boiling point separately, distilling these phosphazene derivatives of to purify.And, when filtering out the by-product salt that produces by fluorination reaction such as NaCl the solution of phosphazene derivative and recovered solvent when in fluorination reaction, recycling from removing through distillation, it is faster than using novel solvent that reaction rate becomes, this is because kept a small amount of phosphazene derivative that distillation fails to remove in the solvent, and this phosphazene derivative has formed the nuclear in the fluorination reaction.
Preparing wherein all A 3For the general formula (V) of NHR with (VII) in the situation of phosphazene derivative, preferred wherein all A that use 2Be the general formula (III) of Cl and (VI) phosphazene derivative.In this case, can save above-mentioned fluorination reaction step, and can obtain target compound with lower cost.Preparing wherein all A 3In the situation for general formula (V) phosphazene derivative of NHR, the consumption of primary amine is preferably the phosphazene derivative of 9 moles/per 1 mole of general formula (III), and at preparation all A wherein 3In the situation for general formula (VII) phosphazene derivative of NHR, the consumption of primary amine is preferably the phosphazene derivative of 7.5 moles/per 1 mole of general formula (VI).
In solvent, carry out first step.As solvent, that can mention has polar solvent such as oxolane (THF), N, dinethylformamide, acetonitrile etc. and non-polar solven such as a hexane etc.When the number of amino groups that will introduce is big, preferably use polar solvent, because can be with the synthetic target product of high yield, and the number of amino groups that will introduce hour be preferably used non-polar solven, because can be with the synthetic target product of high yield.Solvent load is preferably per 1 mole of general formula of 100-1000mL/ (III) or phosphazene derivative (VI).And solvent can reuse after reclaiming.As the advantage of circulation, can mention that environmental friendliness, reaction carry out fast etc.
In order to quicken the reaction of general formula (III) or phosphazene derivative (VI) and general formula (IV) primary amine, when the reaction beginning, need heat.Heating-up temperature is preferably 50-80 ℃.In case the control reaction is wished in the reaction beginning, maintains about 60 ℃, because it is exothermic reaction.For heating time, consider above-mentioned heating time, select the time of enough reacting aptly.For example, when using THF to make solvent, preferred reaction was carried out under about 60 ℃ about 10 hours.After reaction is finished, reactant liquor was displayed about 1 day, from reaction system, remove hydrogen fluoride or hydrochloric acid that above-mentioned reaction produces afterwards.Simultaneously, filter out the primary amine fluoride salt or the chloride salt of precipitation.
In second step, in general formula (V) or phosphazene derivative (VII), add pure lithium salts, preparation general formula (I) or the compound of (II) representing.
As pure lithium salts, that can mention has lithium methoxide, a lithium ethoxide etc.Wherein, the particular methanol lithium is because it is reactive high.The consumption of alcohol lithium salts is preferably 1.5-12 mole/per 1 mole of general formula (V) or phosphazene derivative (VII).Consider that the lithium as target replaces number, selects this consumption aptly, and is preferably the 1.5-2 times of equivalent that is equivalent to replace number.
In addition, second step is exothermic reaction, thereby keeps the temperature of reaction system at 20-50 ℃ when preferably reacting.
After the reaction of finishing between general formula (V) or phosphazene derivative (VII) and the pure lithium salts, can be by the method separation general formula (I) of for example recrystallization or the compound of (II) representing.
＜battery with nonaqueous electrolyte 〉
Battery with nonaqueous electrolyte of the present invention comprises positive pole, negative pole and comprises proton-inert organic solvent and the electrolyte of above-mentioned supporting electrolyte, and if desired, also is provided at parts commonly used in the battery with nonaqueous electrolyte technical field such as division board etc.
-anodal-
Positive electrode in the battery with nonaqueous electrolyte of the present invention is some difference between primary cell and secondary cell.For example as the positive pole of nonaqueous electrolytic solution primary cell, that preferably can mention has a fluorographite ((CF x) n), MnO 2(but its electrochemistry or chemical synthesis), V 2O 5, MoO 3, Ag 2CrO 4, CuO, CuS, FeS 2, SO 2, SOCl 2, TiS 2Deng.Wherein, preferred MnO 2, V 2O 5And fluorographite, because its capacity height, fail safe is good, discharge potential is high and outstanding to electrolytical wettability, and consider more preferably MnO from the cost angle 2And V 2O 5These materials can use separately or two or more are used in combination.
As the positive pole of nonaqueous electrolytic solution secondary battery, that preferably can mention has metal oxide such as a V 2O 5, V 6O 13, MnO 2, MnO 3Deng; Lithium-contained composite oxide such as LiCoO 2, LiNiO 2, LiMn 2O 4, LiFeO 2, LiFePO 4Deng; Metal sulfide such as TiS 2, MoS 2Deng; Electric conductive polymer such as polyaniline etc.Lithium-contained composite oxide can be to comprise two or three composite oxides that are selected from the transition metal of Fe, Mn, Co and Ni.In the latter, composite oxides are by LiFe xCo yNi (1-x-y)O 2(wherein 0≤x＜1,0≤y＜1,0＜x+y≤1), LiMn xFe yO 2-x-yDeng expression.Wherein, preferred especially LiCoO 2, LiNiO 2, LiMn 2O 4, because its capacity height, safe and outstanding to electrolytical wettability.These materials can use separately or two or more are used in combination.
If desired, positive pole can mix with conductivity reagent and adhesive.As conductivity reagent, that can mention has acetylene black etc., and as adhesive, and that can mention has polyvinylidene fluoride (PVDF), a polytetrafluoroethylene (PTFE) etc.In the situation that adopts these additives, they are sneaked into the ratio of sneaking into identical in the regular situation, for example, and positive electrode: conductivity reagent: adhesive=8: 1: 1-8: 1: 0.2 (quality ratio).
Anodal shape is not particularly limited, and can be selected from the electrode shape of knowing aptly.That for example, can mention has sheet, column, plate-like, a helical form etc.
-negative pole-
Negative material in the battery with nonaqueous electrolyte of the present invention is some difference between primary cell and secondary cell.For example, as the negative pole of nonaqueous electrolytic solution primary cell, that can mention has lithium metal itself, a lithium alloy etc.As with the metal of lithium component alloy, that can mention has Sn, Pb, Al, Au, Pt, In, Zn, Cd, Ag, a Mg etc.Wherein, consider preferred Al, Zn and Mg from the angle of relatively large deposition and toxicity.These materials can use separately or two or more are used in combination.
As the negative pole of nonaqueous electrolytic solution secondary battery, the alloy that lithium metal itself, lithium and Al, In, Pb, Zn etc. are arranged that can mention, carbonaceous material is as graphite of mixing lithium etc.Wherein, consider preferred carbonaceous material such as graphite etc. from the angle of greater security.These materials can use separately or two or more are used in combination.
The negative pole shape is not particularly limited, and can be selected from the anodal equiform form of knowing of picture aptly.
-nonaqueous electrolytic solution-
The electrolyte that is used for battery with nonaqueous electrolyte of the present invention comprises proton-inert organic solvent and above-mentioned supporting electrolyte.Up to now, in based on the electrolyte of proton-inert organic solvent, caused above-mentioned safety problem.Yet, the electrolyte that comprises supporting electrolyte of the present invention and proton-inert organic solvent can not be higher than inhibition evaporation-decomposition under about 200 ℃ lower temperature, and reduce the danger of ignition, because supporting electrolyte is to be the compound of basic framework with the phosphazene derivative, the effect that suppresses burning is arranged.Simultaneously, even because negative material fusing etc. cause igniting at inside battery, the danger of catching fire is also low.In addition, because phosphorus has the effect of the high molecular weight material chain decomposition that suppresses the formation battery, therefore also reduced the danger of ignition effectively.
The preferred limited oxygen index (limit oxygen index) that adds the electrolyte of supporting electrolyte is not less than 21 volume %.When limited oxygen index was lower than 21 volume %, the effect of inhibition point fire burns was not enough.Term used herein " limited oxygen index " refers to keep the value of the needed minimum oxygen concentration of substance combustion under the fc-specific test FC condition of JIS K7201 definition, represent with percent by volume, wherein limited oxygen index is low more, the danger of ignition is high more, and on the contrary, limited oxygen index is high more, and the danger of ignition is low more.In the present invention, according to JIS K7201 measuring limit oxygen index, the danger of evaluation point fire burns.
Limited oxygen index under atmospheric conditions should be 20.2 volume % mutually, and therefore the limited oxygen index of 20.2 volume % means in atmosphere and can burn.The inventor has done various researchs, finds to show self-extinguishment when limited oxygen index is not less than 21 volume %, shows anti-flammability when being not less than 23 volume %, and showing incombustibility when being not less than 25 volume %.And, term used herein " self-extinguishment; anti-flammability; incombustibility " defines in the method according to UL 94HB method, wherein when preparing the sample of 127 * 12.7mm by perfusion 1.0mL electrolyte in combustible quartz fibre and in atmospheric environment, lighting a fire, self-extinguishment is meant that the object that extinguishes in the scope of ignition flame between 25mm and 100mm and fall from network can not catch fire, anti-flammability is meant that ignition flame can not arrive the 25mm place of device and the object that falls from network can not catch fire, and incombustibility is meant and does not observe igniting (burning length: 0mm).
-proton-inert organic solvent-
Lithium or lithium alloy reaction that the proton-inert organic solvent of the formation electrolyte in battery with nonaqueous electrolyte of the present invention is not used with negative pole.To not restriction especially of aprotic solvent, but consider, comprise ether compound, ester compounds etc. from viscosity to the angle of low value of control electrolyte.Particularly, that preferably can mention has 1,2-dimethoxy-ethane (DME), oxolane, dimethyl carbonate, diethyl carbonate (DEC), diphenyl carbonate, ethylene carbonate ester (EC), propylene glycol carbonate (PC), gamma-butyrolacton (GBL), gamma-valerolactone, methyl ethyl carbonate, ethylene methyl esters etc.
Wherein, when being used for the nonaqueous electrolytic solution primary cell, preferred cyclic ester compounds such as propylene glycol carbonate, gamma-butyrolacton etc., chain ester compounds such as dimethyl carbonate, methyl ethyl carbonate etc., with the chain ether compound as 1,2-dimethoxy-ethane etc., and when being used for nonaqueous electrolytic solution secondary battery, preferred cyclic ester compounds such as ethylene carbonate ester, propylene glycol carbonate, gamma-butyrolacton etc., chain ester compounds such as dimethyl carbonate, ethylene methyl esters, diethyl carbonate etc., with the chain ether compound as 1,2-dimethoxy-ethane etc.High and the outstanding angle of the dissolubility of above-mentioned supporting electrolyte considered from dielectric constant, preferred cyclic ester compounds is low and therefore make the low angle of electrolyte viscosity consider preference chain ester compounds and chain ether compound from viscosity.They can use separately or two or more are used in combination.
Based on every 1L proton-inert organic solvent, the preferred 0.1-1mol of supporting electrolyte content in the electrolyte, more preferably 0.2-1mol.When content is lower than 0.1mol, can not guarantee the conductivity that electrolyte is enough, therefore and cause the trouble of battery discharge characteristic aspect, and when it surpasses 1mol, the viscosity of nonaqueous electrolytic solution rises and can not guarantee the mobility that lithium ion is enough, thereby equally with above-mentioned situation can not guarantee the conductivity that electrolyte is enough, consequently, solution resistance rises and causes the trouble of original battery discharge characteristic aspect or secondary cell discharge charge characteristic aspect.
-phosphazene derivative and phosphazene derivative isomers-
Preferably in proton-inert organic solvent, add the isomers of phosphazene derivative and/or phosphazene derivative.By using the above-mentioned danger that the supporting electrolyte that suppresses combustion can reduce the battery ignition that has, and by in aprotic solvent, adding phosphazene derivative and/or phosphazene derivative isomery physical efficiency further reduces this danger.
Because identical with supporting electrolyte, phosphazene derivative and phosphazene derivative isomery physical efficiency reduce the danger of battery ignition.In addition, even in the accident burning, the phosphazene derivative and the phosphazene derivative isomers that contain halogen (as fluorine) also can play the active group agent for capturing, and phosphazene derivative and phosphazene derivative isomers with organic substituent have the effect of shielding oxygen, because can generate carbide (coke) on electrode material, it becomes aflame slider.In addition, phosphazene derivative and phosphazene derivative isomers have the effect that suppresses tree formation, even in recharging process, thereby the system of comparing and not adding phosphazene derivative and phosphazene derivative isomers, it is higher that fail safe becomes.
The phosphazene derivative that adds in the subtend proton-inert organic solvent has no particular limits.But, consider from the angle that the dissolving of the relatively low and supporting electrolyte of viscosity is good, preferably be no more than 300mPas (300cP) and by the following general formula (VIII) or (IX) phosphazene derivative of expression 25 ℃ of following viscosity.In this phosphazene derivative, most preferred viscosity is no more than the phosphazene derivative of 5mPas.
Figure C0381718600231
(R wherein 1, R 2And R 3Be monovalence substituting group or halogen independently, X 1For comprising the substituting group of at least a element that is selected from carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulphur, selenium, tellurium and polonium, Y 1, Y 2And Y 3Be divalent linker, diad or singly-bound independently)
(NPR 4 2) n ......(IX)
(R wherein 4Be monovalence substituting group or halogen independently, n is 3-15).
The viscosity of phosphazene derivative under 25 ℃ that requires general formula (VIII) or (IX) represent is no more than 300mPas, and preferably is no more than 100mPas (100cP), further preferably is no more than 5mPas (5cP).When being used for the nonaqueous electrolytic solution primary cell, special preferred viscosities is no more than 20mPas (20cP), and further preferably is no more than 5mPas (5cP).When viscosity surpasses 300mPas (300cP), supporting electrolyte dissolves hardly, and the wettability to positive electrode, dividing plate etc. reduces, and, especially can not use not being higher than under the lower temperature conditions such as solidifying point because the increase of electrolyte viscosity resistance causes having reduced largely ionic conductivity.
In general formula (VIII), R 1, R 2And R 3Except being monovalence substituting group or the halogen, be not particularly limited.As the monovalence substituting group, that can mention has alkoxyl, alkyl, carboxyl, acyl group, an aryl etc.Wherein, low and make the low angle of electrolyte viscosity consider from viscosity, preferred alkoxyl.On the other hand, as halogen, that preferably can mention has fluorine, chlorine, a bromine etc.All R 1-R 3Can be identical substituting group, perhaps a part wherein be different substituting group.
As alkoxyl, the alkoxyl such as methoxy ethoxy, the methoxy ethoxy ethyoxyl etc. that have methoxyl group, ethyoxyl, propoxyl group, butoxy and alkoxyl to replace that can mention.Wherein, preferably all R 1-R 3Be methoxyl group, ethyoxyl, methoxy ethoxy or methoxy ethoxy ethyoxyl, and consider, preferred especially methoxy or ethoxy from the angle of low viscosity and high-k.
As alkyl, that can mention has methyl, ethyl, propyl group, butyl, an amyl group etc.As acyl group, that can mention has formoxyl, acetyl group, propiono, bytyry, isobutyryl, a valeryl etc.As aryl, that can mention has phenyl, tolyl, a naphthyl etc.
In these monovalence substituting groups, preferably replace protium with halogen.As halogen, preferred fluorine, chlorine and bromine, wherein preferred especially fluorine, its less preferred chlorine.Replace than chlorine, replace the monovalence substituting group of protium often bigger aspect the effect of improving the secondary cell cycle characteristics with fluorine.
Y as general formula (VIII) 1, Y 2And Y 3Shown divalent linker, that can mention has a CH 2Base and the divalent linker that contains at least a element that is selected from oxygen, sulphur, selenium, nitrogen, boron, aluminium, scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium, polonium, tungsten, iron, cobalt and nickel.Wherein, preferred CH 2Base and contain the divalent linker of at least a element that is selected from oxygen, sulphur, selenium and nitrogen and especially preferably contains the divalent linker of sulphur and/or selenium.Simultaneously, Y 1, Y 2And Y 3Can be diad such as oxygen, sulphur, selenium etc., perhaps singly-bound.All Y 1-Y 3Can be identical, perhaps a part wherein is different mutually.
In general formula (VIII), consider preferred X from harmfulness, environmental friendliness equal angles 1For containing the substituting group of at least a element that is selected from carbon, silicon, nitrogen, oxygen and sulphur.In these substituting groups, more preferably have following general formula (XV), (XVI) or (XVII) shown in the substituting group of structure.
(at general formula (XV), (XVI) with (XVII), R 10-R 14Be monovalence substituting group or halogen independently, Y 10-Y 14Be divalent linker, diad or singly-bound independently, Z 1Be divalent group or diad.)
As (XV), (XVI) with the R (XVII) 10-R 14, that preferably can mention has a R with general formula (VIII) 1-R 3Described in identical monovalence substituting group or halogen.Simultaneously, they can be identical in identical substituting group, and perhaps a part wherein is different mutually.R in the general formula (XV) 10And R 11, and the R in the general formula (XVII) 13And R 14Keyed jointing forms ring mutually.
As (XV), (XVI) with the Y (XVII) 10-Y 14, that can mention has a Y with general formula (VIII) 1-Y 3Described in identical divalent linker, diad etc.Similarly, the group of preferred especially sulfur-bearing and/or selenium is because can reduce the danger of electrolyte ignition.They can be identical in identical substituting group, and perhaps a part wherein is different mutually.
As the Z in the general formula (XV) 1, that can mention has a CH 2Base, CHR ' base (R ' be alkyl, alkoxyl, phenyl etc.), NR ' base and contain the bilvalent radical of at least a element that is selected from oxygen, sulphur, selenium, nitrogen, boron, aluminium, scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium, polonium, tungsten, iron, cobalt and nickel.Wherein, preferred CH 2Base, CHR ' base, NR ' base and contain at least a divalent group that is selected from the element of oxygen, sulphur and selenium.Especially, preferably contain the group of sulphur and/or selenium, because can reduce the danger of electrolyte ignition.Simultaneously, Z 1Can be diad such as oxygen, sulphur, selenium etc.
In these substituting groups, consider the phosphorous substituting group shown in the special preferred formula (XV) from the angle of effective reduction ignition.Simultaneously, when substituting group is sulfur-bearing substituting group shown in the general formula (XVI), consider that from the angle that the electrolyte interface resistance is reduced it is particularly preferred.
In general formula (IX), R 4Except being monovalence substituting group or the halogen, be not particularly limited.As the monovalence substituting group, that can mention has alkoxyl, alkyl, carboxyl, acyl group, an aryl etc.Wherein, consider preferred alkoxyl from the angle that electrolyte viscosity is reduced.As halogen, that preferably can mention has fluorine, chlorine, a bromine etc.As alkoxyl, that can mention has methoxyl group, ethyoxyl, methoxy ethoxy, propoxyl group, a phenoxy group etc.Wherein, when being used for the nonaqueous electrolytic solution primary cell, preferred especially methoxyl group, ethyoxyl, positive propoxy, phenoxy group, and when being used for nonaqueous electrolytic solution secondary battery, preferred especially methoxyl group, ethyoxyl, methoxy ethoxy and phenoxy group.In these monovalence substituting groups, preferably replace protium with halogen.As halogen, that preferably can mention has fluorine, chlorine, a bromine etc.As the substituting group that replaces with fluorine, that can mention for example has a trifluoro ethoxy.
By suitably selecting the R among general formula (VIII), (IX), (XV)-(XVII) 1-R 4, R 10-R 14, Y 1-Y 3, Y 10-Y 14And Z 1, can prepare the electrolyte that has preferred viscosity, is suitable for adding the solubility etc. of mixing.These phosphazene derivatives can use separately also and can two or more be used in combination.
In the phosphazene derivative of general formula (IX), the low-temperature characteristics of improving battery and the angle of further improving electrolytical fail safe are considered from electrolytical viscosity is reduced, the phosphazene derivative of preferred especially following general formula (X) expression.
(NPF 2) n .....(X)
(wherein n is 3-13).
The phosphazene derivative of general formula (X) is a low-viscosity (mobile) liquid under room temperature (25 ℃), and has the effect that reduces solidifying point.By in electrolyte, adding this phosphazene derivative, can give electrolyte outstanding low-temperature characteristics, electrolytical viscosity is reduced, the battery with nonaqueous electrolyte with low internal resistance and high conductivity can be provided.Therefore, may provide the battery with nonaqueous electrolyte that demonstrates outstanding discharge performance for a long time, even to be used for especially under low temp area or the mid-season cryogenic conditions also be like this for it.
In general formula (X), consider that from the angle of giving the outstanding low-temperature characteristics of electrolyte and electrolyte viscosity is reduced n is preferably 3-4, more preferably 3.When n value hour, the performance that boiling point reduces and prevents from can improve near flame the time to light a fire.And when the n value becomes big, even the elevation of boiling point and at high temperature electrolyte also can stably use.In order to utilize above-mentioned characteristic to obtain target capabilities, can suitably select and use multiple phosphazene derivative.
By suitably selecting the n value in the general formula (X), can prepare to have the electrolyte of preferred viscosity, the solubility that is suitable for mixing, low-temperature characteristics etc.These phosphazene derivatives can use separately also and can two or more be used in combination.
The viscosity of general formula (X) phosphazene derivative is not particularly limited except being no more than 20mPas (20cP), but considers from the angle of improving conductivity and low-temperature characteristics, preferably is no more than 10mPas (10cP), more preferably no more than 5mPas (5cP).In addition, use viscosity measuring instrument (R type viscosity apparatus Model RE500-SL, Toki Sangyo Co., Ltd makes) under each rotating speed of 1rpm, 2rpm, 3rpm, 5rpm, 7rpm, 10rpm, 20rpm and 50rpm, measured 120 seconds, rotating speed viscosity down when measuring indicated value and be 50-60% as analysis condition, definite thus viscosity of the present invention.
In the phosphazene derivative of general formula (IX), consider the phosphazene derivative of preferred especially following general formula (XI) expression from the angle of the fail safe that improves electrolyte:
(NPR 5 2) n .....(XI)
(R wherein 5Be monovalence substituting group or halogen independently, and all R 5In at least one be fluorine-containing monovalence substituting group or fluorine, n is 3-8, but not all R 5All be fluorine).
When containing the phosphazene derivative of general formula (XI), can give outstanding self-extinguishment of electrolyte or anti-flammability, improve the fail safe of electrolyte.When using wherein all R 5At least one when being the substituent general formula of fluorine-containing monovalence (XI) phosphazene derivative, can give electrolyte more outstanding fail safe.When using wherein all R 5At least one when being general formula (XI) phosphazene derivative of fluorine, can give electrolyte further outstanding fail safe.That is to say, than not fluorine-containing phosphazene derivative, all R wherein 5At least one general formula (XI) phosphazene derivative for fluorine-containing monovalence substituting group or fluorine have the electrolyte of making effect of combustion hardly, can give electrolyte more outstanding fail safe.
And, all R wherein 5For fluorine and n are that 3 general formula (XI) phosphazene derivative is non-flammable, and prevent the good effect of lighting a fire when having near flame, but its boiling point is very low, if it evaporates fully, remaining proton-inert organic solvent etc. can burn up.
As the monovalence substituting group in the general formula (XI), that can mention has alkoxyl, alkyl, acyl group, aryl, a carboxyl etc., considers preferred alkoxyl from the angle of the good fail safe that improves electrolyte.As alkoxyl, the alkoxyl that methoxyl group, ethyoxyl, positive propoxy, isopropoxy, butoxy and alkoxyl replacement are arranged that can mention such as methoxy ethoxy etc.Particularly, consider preferred methoxyl group, ethyoxyl and positive propoxy from the fabulous angle of improving the electrolyte fail safe.Simultaneously, consider preferred methoxyl group from the angle that electrolyte viscosity is reduced.
In general formula (XI), consider that from the angle of giving the outstanding fail safe of electrolyte n is preferably 3-4.
Preferred monovalence substituting group has fluorine to replace.Not all R in general formula (XI) 5When all being fluorine, at least one monovalence substituting group contains fluorine.
Fluorine content in the phosphazene derivative is preferably 3-70 weight %, more preferably 7-45 weight %.When content is in above-mentioned digital scope, can preferably give electrolyte " outstanding fail safe ".
As the molecular structure of the phosphazene derivative of general formula (XI), defluorination is outer can also to contain halogen such as chlorine, bromine etc.But, fluorine most preferably, its less preferred chlorine.Than containing chlorine derivative, fluorine-containing derivant often has the bigger effect of improving the secondary cell cycle characteristics.
By suitably selecting the R in the general formula (XI) 5With the n value, can prepare the electrolyte of solubility of having preferred fail safe and viscosity, being suitable for mixing etc.These phosphazene derivatives can use separately also and can two or more be used in combination.
The viscosity of the phosphazene derivative of general formula (XI) is not particularly limited except being no more than 20mPas (20cP), but considers from the angle of improving conductivity and low-temperature characteristics, preferably is no more than 10mPas (10cP), more preferably no more than 5mPas (5cP).
As the phosphazene derivative that in proton-inert organic solvent, adds, from improving the electrolyte fail safe and controlling the angle that electrolyte viscosity raises simultaneously and consider, preferably 25 ℃ (room temperatures) down for solid and by the phosphazene derivative of following general formula (XII) expression.
(NPR 6 2) n .....(XII)
(R wherein 6Be monovalence substituting group or halogen independently, n is 3-6).
Because the phosphazene derivative of general formula (XII) is solid down in room temperature (25 ℃), therefore when it joined in the electrolyte, it was dissolved in the viscosity that electrolyte has improved electrolyte.But if addition is the specified quantitative of mentioning later, then the ratio that raises of electrolyte viscosity is low but the battery with nonaqueous electrolyte with low internal resistance and high conductivity can be provided.Simultaneously, the phosphazene derivative of general formula (XII) is dissolved in electrolyte, and the long-time stability of electrolyte are outstanding.
In general formula (XII), R 6Except being monovalence substituting group or the halogen, be not particularly limited.As the monovalence substituting group, that can mention has alkoxyl, alkyl, carboxyl, acyl group, an aryl etc.As halogen, that preferably can mention has halogen such as fluorine, chlorine, bromine, iodine etc.From suppressing the angle consideration that electrolyte viscosity raises, preferred especially alkoxyl.From suppressing the angle consideration that electrolyte viscosity raises, alkoxyl is preferably methoxyl group, ethyoxyl, methoxy ethoxy, propoxyl group (isopropoxy, positive propoxy), phenoxy group, trifluoro ethoxy etc., more preferably methoxyl group, ethyoxyl, propoxyl group (isopropoxy, positive propoxy), phenoxy group and trifluoro ethoxy.Preferred monovalence substituting group contains above-mentioned halogen.
In general formula (XII), from suppressing the angle consideration that electrolyte viscosity raises, preferred especially n is 3 or 4.
As the phosphazene derivative of general formula (XII), from suppressing the angle consideration that electrolyte viscosity raises, the R in the special preferred formula (XII) 6For methoxyl group and n are 3 structure, the R in the general formula (XII) 6Be at least methoxyl group or phenoxy group and n and be 4 structure, the R in the general formula (XII) 6For ethyoxyl and n are 4 structure, the R in the general formula (XII) 6For isopropoxy and n are 3 or 4 structure, the R in the general formula (XII) 6For positive propoxy and n are 4 structure, the R in the general formula (XII) 6For trifluoro ethoxy and n are 3 or 4 structure, the R in the general formula (XII) 6It for phenoxy group and n 3 or 4 structure.
By suitably selecting each substituting group and n value in the general formula (XII), can prepare the electrolyte of solubility of having preferred viscosity, being suitable for mixing etc.These phosphazene derivatives can use separately also and can two or more be used in combination.
The phosphazene derivative isomers that adds in the subtend proton-inert organic solvent is not particularly limited, but consider from the angle of the low-temperature characteristics of improving battery with nonaqueous electrolyte and the fail safe that further improves electrolyte, the isomers of preferred following general formula (XIII) expression, it is the isomers of the phosphazene derivative of following general formula (XIV) expression.
Figure C0381718600301
(at general formula (XIII) with (XIV), R 7, R 8And R 9Be monovalence substituting group or halogen independently, X 2For comprising the substituting group of at least a element that is selected from carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulphur, selenium, tellurium and polonium, Y 7, Y 8And Y 9Be divalent linker, diad or singly-bound independently).
In general formula (XIII), R 7, R 8And R 9Except being monovalence substituting group or the halogen, be not particularly limited.As the monovalence substituting group, that can mention has alkoxyl, alkyl, carboxyl, acyl group, an aryl etc.As halogen, that preferably can mention has halogen such as fluorine, chlorine, bromine etc.Wherein, consider preferred especially fluorine, alkoxyl etc. from the angle of electrolytical low-temperature characteristics and electrochemical stability.Simultaneously, consider preferred alkoxyl, fluoroalkoxy etc. from the angle that electrolyte viscosity is reduced.All R 7-R 9Can be identical substituting group, perhaps wherein a part be different substituting group.
As alkoxyl, the alkoxyl such as methoxy ethoxy, the methoxy ethoxy ethyoxyl etc. that for example have methoxyl group, ethyoxyl, propoxyl group, butoxy and alkoxyl to replace that can mention.Wherein, preferably all R 7-R 9Be methoxyl group, ethyoxyl, methoxy ethoxy or methoxy ethoxy ethyoxyl, and consider that from the angle of low viscosity and high-k preferred all especially all is methoxy or ethoxy.As alkyl, that can mention has methyl, ethyl, propyl group, butyl, an amyl group etc.As acyl group, that can mention has formoxyl, acetyl group, propiono, bytyry, isobutyryl, a valeryl etc.As aryl, that can mention has phenyl, tolyl, a naphthyl etc.In these substituting groups, preferably replace protium with halogen.As halogen, that preferably can mention has fluorine, chlorine, a bromine etc.
In general formula (XIII), as Y 7And Y 8Shown divalent linker, that can mention has a CH 2Base and the divalent linker that contains at least a element that is selected from oxygen, sulphur, selenium, nitrogen, boron, aluminium, scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium, polonium, tungsten, iron, cobalt and nickel.Wherein, preferred CH 2Base and the divalent linker that contains at least a element that is selected from oxygen, sulphur, selenium and nitrogen.Simultaneously, Y 7And Y 8Can be diad such as oxygen, sulphur, selenium etc., perhaps singly-bound.Particularly, consider from the angle of improving the electrolyte fail safe, divalent linker, oxygen element and the element sulphur of preferred sulfur-bearing and/or oxygen, and consider preferred oxygen containing divalent linker and oxygen element from the outstanding angle of electrolyte low-temperature characteristics.Y 7And Y 8Can be identical or different.
As the X in the general formula (XIII) 2, consider from toxicity, environment equal angles, preferably contain at least a substituting group that selects element from carbon, silicon, nitrogen, oxygen and sulphur, more preferably have following general formula (XVIII), (XIX) or (XX) shown in the substituting group of structure.
Figure C0381718600311
(at general formula (XVIII), (XIX) with (XX), R 15-R 19Be monovalence substituting group or halogen independently, Y 15-Y 19Be divalent linker, diad or singly-bound independently, Z 2Be divalent group or diad.)
As (XVIII), (XIX) with the R (XX) 15-R 19, that preferably can mention has a R with general formula (XIII) 7-R 8Described in identical monovalence substituting group or halogen.Simultaneously, they can be identical in identical substituting group, and perhaps a part wherein is different mutually.In addition, the R in the general formula (XVIII) 15And R 16And the R in the general formula (XX) 18And R 19Keyed jointing forms ring mutually.
As formula (XVIII), (XIX) with the Y (XX) 15-Y 19, that can mention has a Y with general formula (XIII) 7-Y 8Described in identical divalent linker, diad etc.Similarly, consider, especially preferably get divalent linker, oxygen element or the element sulphur of sulfur-bearing and/or oxygen from the angle of improving the electrolyte fail safe.Simultaneously, consider, preferably get oxygen containing divalent linker or oxygen element from the angle that the electrolyte low-temperature characteristics is outstanding.They can be identical in identical substituting group, and perhaps a part wherein is different mutually.
As the Z in the general formula (XVIII) 2, that can mention has a CH 2Base, CHR ' base (R ' be alkyl, alkoxyl, phenyl etc.), NR ' base and contain the divalent group of at least a element that is selected from oxygen, sulphur, selenium, nitrogen, boron, aluminium, scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium, polonium, tungsten, iron, cobalt and nickel.Wherein, preferred CH 2Base, CHR ' base, NR ' base and the divalent group that contains at least a element that is selected from oxygen, sulphur and selenium.Simultaneously, Z 2Can be diad such as oxygen, sulphur, selenium etc.Special formula is considered from the angle of improving the electrolyte fail safe, preferably contains divalent group, element sulphur or the selenium element of sulphur and/or selenium.In addition, consider preferred oxygen containing bilvalent radical or oxygen element from the outstanding angle of electrolyte low-temperature characteristics.
In these substituting groups, consider the phosphorous substituting group shown in the special preferred formula (XVIII) from effective angle of improving fail safe.In addition, each Z in general formula (XVIII) 2, Y 15And Y 16During for oxygen element, especially can in electrolyte, demonstrate very outstanding low-temperature characteristics.In addition, when substituting group is sulfur-bearing substituting group shown in the general formula (XIX), consider that from the angle that the electrolyte interface resistance is reduced it is preferred.
By suitably select general formula (XIII), (XVIII), (XIX) and (XX) in R 7-R 9, R 15-R 19, Y 7-Y 8, Y 15-Y 19And Z 2, can prepare the electrolyte of the solubility that has preferred viscosity, be suitable for adding-mix, low-temperature characteristics etc.These compounds can use separately also and can two or more be used in combination.
The isomers of general formula (XIII) expression is the isomers of the phosphazene derivative of general formula (XIV) expression, and it can prepare by adjusting vacuum degree and/or temperature in the process of the phosphazene derivative that forms general formula (XIV).Can measure content of isomer (volume %) in the electrolyte by following method of measurement.
" method of measurement "
It can be measured by the following method: the peak area of finding out sample by gel permeation chromatography (GPC) or high-speed liquid chromatography, the area of this peak area with every mole of isomers finding out in advance compared, draw a molar ratio, further consider that then proportion is translated into volume.In addition, it can also pass through gas Chromatographic Determination.
As the phosphazene derivative of general formula (XIV) expression, preferred viscosities is relatively low can dissolve well with supporting electrolyte.As the R in the general formula (XIV) 7-R 9, Y 7-Y 8And X 2, that preferably can mention has a R with general formula (XIII) 7-R 9, Y 7-Y 8And X 2Explanation described in identical those.
Isomers as general formula (VIII), (IX), (XII) or the phosphazene derivative of (XIV) representing or general formula (XIII) expression preferably contains the substituting group that comprises halogen in its molecular structure.When existence in the molecular structure comprises the substituting group of halogen,, also can reduce the danger of electrolyte ignition effectively by its halogen gas that derives even the content of phosphazene derivative or isomers is little.In addition, comprise in the substituting group of compound in the situation of halogen, the appearance of halogen free radical can bring problem.But, in the situation of the isomers of above-mentioned phosphazene derivative or phosphazene derivative, can not cause this problem, because the P elements in the molecular structure can be caught halogen free radical base, form stable phosphorus Halides.
Content of halogen in phosphazene derivative or the phosphazene derivative isomers is preferably 2-80 weight %, more preferably 2-60 weight %, further preferred 2-50 weight %.When content is lower than 2 weight %, can not demonstrate enough because of comprising the effect that halogen obtains, and when it surpassed 80 weight %, when adding in the electrolyte, viscosity can uprise and conductivity can reduce.As halogen, preferred fluorine, chlorine, bromine etc., and from obtaining the angle consideration of good battery behavior, preferred especially fluorine.
At general formula (VIII), (IX), (XI), (XII) with (XIV) in the phosphazene derivative of expression, flash-point is not particularly limited, but considers from the angle of control burning etc., preferably is not less than 100 ℃, more preferably be not less than 150 ℃, further preferably be not less than 300 ℃.On the other hand, the phosphazene derivative of general formula (X) expression does not have flash-point.Term used herein " flash-point " refers to that flame is expanded and the temperature when covering at least 75% material surface on material surface.Flash-point is to weigh the index that forms the trend of combustible mixture with air mixed.When the flash-point of phosphazene derivative is not less than 100 ℃ or when not having flash-point, can suppress burning etc., and if cause burning etc. at inside battery, it can reduce the danger that causes the violent burning of electrolyte surface because of igniting.
The content of phosphazene derivative or phosphazene derivative isomers is as follows in the nonaqueous electrolytic solution.Consider from the angle of " limited oxygen index ", electrolyte formula of (VIII) or (IX) content of the phosphazene derivative of expression preferably be not less than 5 volume %, more preferably 10-50 volume %.By regulating the danger that content value can reduce the electrolyte ignition to the above-mentioned digital scope effectively.Although can effectively reduce the danger of burning, this content range according to the kind of supporting electrolyte with used electrolytical kind and different.Particularly, by suitably selecting the used system of content optimization, control viscosity is to minimum and make limited oxygen index be not less than 21 volume %.
Consider from the angle of " fail safe " of electrolyte, the content of the phosphazene derivative of general formula (X) preferably is not less than 5 volume %, the content of the phosphazene derivative of general formula (XI) is not less than 10 volume %, more preferably be not less than 15 volume %, the content of the phosphazene derivative of general formula (XII) preferably is not less than 20 volume %, and the total content of the phosphazene derivative of the isomers of general formula (XIII) and general formula (XIV) preferably is not less than 20 volume %.When content is in above-mentioned digital scope, can preferably improve the fail safe of electrolyte.
The angle of " low-temperature characteristics " from electrolyte is considered, the content of the phosphazene derivative of general formula (X) preferably is not less than 1 volume %, more preferably be not less than 3 volume %, further preferably be not less than 5 volume %, the total content of the phosphazene derivative of the isomers of general formula (XIII) and general formula (XIV) preferably is not less than 1 volume %, more preferably be not less than 2 volume %, further preferred 5 volume %.When content was lower than 1 volume %, the low-temperature characteristics of electrolyte was not enough.
Consider that from the angle of " the viscosity reduction " of electrolyte the content of the phosphazene derivative of general formula (X) preferably is not less than 3 volume %, more preferably 3-80 volume %.When content is lower than 3 volume %, electrolyte viscosity is effectively reduced.
Consider that from the angle of " viscosity raise control " of electrolyte the content of the phosphazene derivative of general formula (XII) preferably is no more than 40 weight %, more preferably no more than 35 weight %, further preferably is no more than 30 weight %.When content surpassed 40 weight %, it is quite big that electrolytical viscosity becomes, and internal resistance uprises, and the conductivity step-down.
-other parts-
As other used in the battery with nonaqueous electrolyte of the present invention parts, that can mention has a dividing plate that inserts between the positive pole and negative pole in the battery with nonaqueous electrolyte, and it prevents the short circuit current that causes because of contact between the electrode.Material as dividing plate, having of can mentioning can guarantee to prevent the material that contact between the electrode and electrolyte can pass or immerse, for example by the adhesive-bonded fabric of preparations such as synthetic resin such as polytetrafluoroethylene, polypropylene, polyethylene, cellulose base resin, polybutylene terephthalate (PBT), PETG, film layer etc.Wherein, special preferred thickness is 20-50 μ m and by the microporous barrier of polypropylene or polyethene preparation with by the film of preparations such as cellulose base resin, polybutylene terephthalate (PBT), PETG.
In the present invention, except aforementioned barriers, can also advantageously use various know be usually used in parts in the battery.
The form of-battery with nonaqueous electrolyte-
Form according to above-mentioned battery with nonaqueous electrolyte of the present invention is not particularly limited, but the column type that the various forms of knowing such as Coin shape, coin shape, paper mold, pentagon, helical structure are arranged that preferably can mention etc.In the situation of coin shape, battery with nonaqueous electrolyte can be by preparation sheet positive pole and negative pole, and between positive pole and negative pole folder upper spacer etc. and preparing.Also have, in the situation of helical structure, battery with nonaqueous electrolyte can be by preparation sheet positive pole, be clipped between the collector electrode, pile up negative pole (sheet) thereon, then its coiling is waited and prepares.
＜polymer battery 〉
Polymer battery of the present invention comprises positive pole, negative pole and comprises the polymer dielectric of above-mentioned supporting electrolyte and polymer, if desired, is usually used in other parts of polymer battery technical field in addition.
-anodal-
Positive pole in the polymer battery of the present invention is not particularly limited, and can be selected from the positive electrode of knowing aptly.That for example, preferably can mention has metal oxide such as a V 2O 5, V 6O 13, MnO 2, MnO 3Deng; Lithium-contained composite oxide such as LiCoO 2, LiNiO 2, LiMn 2O 4, LiFeO 2, LiFePO 4Deng; Metal sulfide such as TiS 2, MoS 2Deng; Electric conductive polymer such as polyaniline etc.Lithium-contained composite oxide can be to comprise two or three composite oxides that are selected from the transition metal of Fe, Mn, Co and Ni.In the latter, composite oxides are by LiFe xCo yNi (1-x-y)O 2(wherein 0≤x＜1,0≤y＜1,0＜x+y≤1), LiMn xFe yO 2-x-yDeng expression.Wherein, from capacity height, safe and the outstanding angle of electrolytical wettability considered preferred especially LiCoO 2, LiNiO 2And LiMn 2O 4These materials can use separately or two or more are used in combination.
If desired, positive pole can mix with conductivity reagent and adhesive.As conductivity reagent, that can mention has acetylene black etc., and as adhesive, and that can mention has polyvinylidene fluoride (PVDF), a polytetrafluoroethylene (PTFE) etc.In the situation that adopts these additives, they are sneaked into the ratio of sneaking into identical in the regular situation, for example, and positive electrode: conductivity reagent: adhesive=8: 1: 1-8: 1: 0.2 (quality ratio).
Anodal form is not particularly limited, and can be selected from the electrode form of knowing aptly.That for example, can mention has sheet, column, plate-like, a helical form etc.Wherein, consider preferred sheet etc. from the thin battery angle.
-negative pole-
Negative pole in the polymer battery of the present invention can reach occlusion and discharge lithium, lithium ion etc.Therefore, except energy occlusion and release lithium, lithium ion etc., its material is not particularly limited, and can be selected from the negative material of knowing aptly.For example, that preferably can mention has a material that contains lithium, is specially lithium metal itself, and the alloy of lithium and aluminium, indium, lead, zinc etc. and material containing carbon are as graphite of mixing lithium etc.Wherein, consider preferred material containing carbon such as graphite etc. from the angle that fail safe is higher.These materials can use separately or two or more are used in combination.The form of negative pole is not particularly limited, and can be selected from the form of knowing as positive polar form aptly.
-polymer dielectric-
Used polymer dielectric comprises the above-mentioned general formula (I) or (II) supporting electrolyte and the polymer of compound of expression in the polymer battery of the present invention, if desired, can also contain other component.
General formula (I) or compound (II) because contain lithium in its molecule and discharge lithium ion in polymer dielectric, can improve the conductivity of polymer dielectric as the ion source of lithium ion.Simultaneously, this compound is basic framework with the phosphazene derivative, thereby it has the effect of control burning.Although soaked into the problem that secure context is arranged in the conventional polymer electrolyte with swelling by proton-inert organic solvent as mentioned above, but be based on the effect of the nitrogen of phosphazene derivative generation, the polymer dielectric that contains above-mentioned supporting electrolyte has self-extinguishment or anti-flammability, thereby has reduced the dangerous of ignition and improved fail safe.In addition,, therefore can provide self-extinguishment or anti-flammability effectively, reduce the danger of ignition because phosphorus has the effect that the chain of the high molecular weight material that suppresses a formation battery part decomposes.
The preferred limited oxygen index that adds the polymer dielectric of above-mentioned supporting electrolyte is not less than 21 volume %.When limited oxygen index was lower than 21 volume %, the effect of inhibition point fire burns was not enough.In addition, the definition of limited oxygen index and method of measurement thereof are as previously mentioned.
-polymer-
Polymer used in the electrolyte of polymer battery of the present invention is not particularly limited, and that can mention has all polymer that are usually used in polymer battery.For example, have poly(ethylene oxide), polyacrylate, PPOX, polyacrylonitrile, contain the polyacrylate of ethylene oxide unit etc.Wherein, consider preferred especially poly(ethylene oxide) and PPOX from the angle that electricity is stable.
The weight average molecular weight of preferred polymers is not less than 100000, particularly is not less than 5000000.When weight average molecular weight is lower than 100000, intensity difference, and it becomes more the state near colloidal sol, rather than gel.
The amount of polymer is preferably 80-95 quality % to the total amount of polymer and supporting electrolyte in the polymer dielectric, more preferably from about 90 quality %.When the amount of polymer was lower than 80 quality %, electrolytical intensity reduced, and when it surpassed 95 quality %, conductivity can reduce.
-other component-
Other component that is comprised in the electrolyte as polymer battery of the present invention, preferred especially proton-inert organic solvent.Because lithium or lithium alloy are used for the negative pole of polymer battery as previously mentioned, and be very high with the reactivity of water, therefore be necessary to use not proton-inert organic solvent with lithium or lithium alloy reaction as the solvent in the injection of polymer electrolyte.Simultaneously, by in polymer dielectric, comprising proton-inert organic solvent, can improve ionic conductivity at an easy rate.
Proton-inert organic solvent is not particularly limited, comprises ether compound, ester compounds etc.That specifically also preferably can mention has 1,2-dimethoxy-ethane (DME), oxolane, dimethyl carbonate, diethyl carbonate (DEC), diphenyl carbonate, ethylene carbonate ester (EC), propylene glycol carbonate (PC), gamma-butyrolacton (GBL), gamma-valerolactone, methyl ethyl carbonate, ethylene methyl esters etc.Wherein, preferred cyclic ester compounds such as ethylene carbonate ester, propylene glycol carbonate, gamma-butyrolacton etc., chain ester compounds such as dimethyl carbonate, ethylene methyl esters, diethyl carbonate etc. and chain ether compound are as 1,2-dimethoxy-ethane etc.Especially, consider preferred cyclic ester compounds, and the low and easy angle consideration of immersion, preference chain ester compounds and ether compound from viscosity from the angle that the solubility of dielectric constant height and above-mentioned supporting electrolyte is outstanding.They can use separately or two or more are used in combination.
The viscosity of proton-inert organic solvent under 25 ℃ is not particularly limited, but preferably is no more than 10mPas (10cP), more preferably no more than 5mPas (5cP).
-phosphazene derivative and phosphazene derivative isomers-
Preferred above-mentioned polymer dielectric further contains the isomers of phosphazene derivative and/or phosphazene derivative.By constituting polymer dielectric with above-mentioned supporting electrolyte with burning inhibition effect, can reduce danger with this electrolytical polymer battery ignition, but, can guarantee to reduce this danger more by phosphazene derivative and/or the phosphazene derivative isomers of in this electrolyte, further comprising as described below.
That is to say that based in reason identical described in the supporting electrolyte, phosphazene derivative and phosphazene derivative isomery physical efficiency reduce the danger of polymer battery ignition.Also have, the phosphazene derivative of halogen-containing (for example fluorine) and phosphazene derivative isomers play the living radical agent for capturing in the accident burning, phosphazene derivative and phosphazene derivative isomers with organic substituent have the effect of shielding oxygen, because it can form carbide (coke) and become aflame slider on electrode material.
In comprising the conventional polymer battery as negative electrode active material such as lithium metal, in discharge process, be dissolved in electrolytical lithium part in recharging and be deposited as dendrite (skeleton) with ionic species, cause problems such as internal short-circuit, blast.But, by in electrolyte, comprising phosphazene derivative and/or phosphazene derivative isomers, can provide safe and battery long service life, wherein can suppress the dendrite deposition effectively, and in battery, not have danger such as internal short-circuit, blast.
Phosphazene derivative that comprises in the electrolyte as polymer battery of the present invention and phosphazene derivative isomers, that can mention has and identical compound described in the above-mentioned battery with nonaqueous electrolyte.Wherein, consider, preferably be liquid down in room temperature (25 ℃) from the effect and the outstanding angle of fail safe of inhibition dendrite deposition, and the chain phosphazene derivative of further preferred formula (VIII) and the ring-type phosphazene derivative of general formula (IX).Simultaneously, electrolytical those that are preferred for battery with nonaqueous electrolyte also are preferred for polymer battery, and be particularly preferred for nonaqueous electrolytic solution secondary battery those be preferred for polymer dielectric.
Consider from suppressing the polymer battery dendrite deposition equal angles especially effectively, preferably R wherein 4For in alkoxyl, phenoxy group and the fluorine at least one, all R 4At least one be general formula (IX) phosphazene derivative of alkoxyl or phenoxy group for fluorine at least one other.
The total amount of phosphazene derivative and phosphazene derivative isomers is as follows in the polymer dielectric.Total amount as phosphazene derivative and phosphazene derivative isomers, according in electrolyte, comprising the effect that phosphazene derivative and/or phosphazene derivative isomers obtain, can mention amount and second amount that energy " is preferably controlled burning " that first can " preferably suppress the dendrite deposition ".
Consider that from the angle of " suppressing the dendrite deposition " total amount of phosphazene derivative in the electrolyte and phosphazene derivative isomers preferably is not less than 0.5 quality %.When total amount was lower than 0.5%, the effect that suppresses the dendrite deposition was not enough.
Consider that from the angle of " control burning " total amount of phosphazene derivative in the electrolyte and phosphazene derivative isomers preferably is not less than 2.5 quality %.When total amount was lower than 2.5%, control electrolyte effect of combustion was not enough.
The method for preparing polymer dielectric of the present invention is not particularly limited, the method that can mention is: with mass ratio (polymer/supporting electrolyte) 9/1 mixed polymer and supporting electrolyte, add volatile solvent and evenly mixing then, and in about 80 ℃ of following uniform dissolution, under vacuum, be heated to about 40 ℃ of evaporating volatile solvents then, and dry, soak into and swelling the acquisition polymer dielectric with proton-inert organic solvent and at least a phosphazene derivative and phosphazene derivative isomers then.As volatile solvent, that can mention has acetonitrile, an alcohols etc.Consider preferred acetonitrile from outstanding solubility equal angles.
Form to polymer dielectric is not particularly limited, but considers preferred sheet from the angle of thin battery.
-other parts-
As other used in the polymer battery of the present invention parts, that can mention has various parts of knowing that are usually used in polymer battery.
The form of-polymer battery-
Form to polymer battery of the present invention is not particularly limited, the column type that the various forms of knowing such as Coin shape, coin shape, paper mold, pentagon, helical structure are arranged that preferably can mention etc.In the situation of helical structure, polymer battery can be by preparation sheet positive pole, be clipped between the collector electrode, pile up negative pole (sheet) thereon, then its coiling etc. is prepared.
Provide the following example explanation the present invention, but do not limit the present invention.
＜supporting electrolyte 〉
(the synthetic embodiment 1 of supporting electrolyte)
The compound of following synthetic following general formula (XXI) expression.At first, in 150mLTHF, add wherein all A 2For general formula (III) phosphazene derivative of Cl [Protein ChemicalCo., Ltd. makes] (50.3g, 0.2mol) and aniline (167g 1.8mol) and at 60 ℃ reacted 10 hours down.Reaction is displayed it 1 day after finishing, and falls the accessory substance hydrochloric acid by heating evaporation then, then by removing by filter aniline hydrochloride.Gained filtrate fully dewatered and add lithium methoxide (76g, 2mol), 45 ℃ of reactions 5 hours down.After reaction is finished, separate and purify, obtain compound (70.3g, 96mmol, the productive rate: 48%) of general formula (XXI) by the method for recrystallization.
Figure C0381718600401
(wherein Ph is a phenyl).
In this synthetic embodiment, 1600-1700cm in the INFRARED ABSORPTION wave spectrum of reaction intermediate (before the lithium methoxide reaction) -1The wide cut that the place observes the NH-deformation vibration absorbs, disappeared but in final product of purifying, should absorb, and at 1080cm -1The place demonstrates the absorption based on the C-N stretching vibration consumingly.Simultaneously, when the Mariner TOF-MS device made from PerSeptive Biosystem Corp. during, observe big mass number peak at 681,625,527,429,331,233 and 135 places at compound that should synthetic embodiment under the ESI ionization conditions at the scope inner analysis of mass number 50-1000.The molecular weight of general formula (XXI) compound is 723, and the fragment quality lose 6 Li or 1-6 NPhLi from compound after is consistent with above-mentioned assay value, thereby judges that the compound that this synthetic embodiment obtains is the compound of general formula (XXI).
(the synthetic embodiment 2 of supporting electrolyte)
The compound of following synthetic following general formula (XXII) expression.At first, in 150mLTHF, add wherein all A 2For general formula (VI) phosphazene derivative of Cl [Nippon kagakuKogyo Co., Ltd. makes] (54g, 0.2mol) and aniline (139g 1.5mol) and at 60 ℃ reacted 10 hours down.The accessory substance hydrochloric acid was displayed 1 day and distilled to reaction with it after finishing, and (57g 1.5mol), reacted 5 hours down at 50 ℃ to add lithium methoxide then.After reaction is finished, separate and purify, obtain compound (69.8g, 0.12mol, the productive rate: 60%) of general formula (XXII) by the method for recrystallization.
Figure C0381718600411
(wherein Ph is a phenyl).
In this synthetic embodiment, 1600-1700cm in the INFRARED ABSORPTION wave spectrum of reaction intermediate (before the lithium methoxide reaction) -1The wide cut that the place observes the NH-deformation vibration absorbs, disappeared but in final product of purifying, should absorb, and at 1080cm -1The place demonstrates the absorption based on C-N stretching vibration consumingly.Simultaneously, when using the compound that the device analysis identical with synthetic embodiment 1 should synthetic embodiment, observe big mass number peak at 547,386,288,190 and 92 places.The molecular weight of the compound of general formula (XXII) is 582, and the fragment quality lose 5 Li or 2-5 NPhLi from compound after is consistent with above-mentioned assay value, thereby judges that the compound that this synthetic embodiment obtains is the compound of general formula (XXII).
(the synthetic embodiment 3 of supporting electrolyte)
In the 150mL acetonitrile, add wherein all A 2For general formula (III) phosphazene derivative of Cl [Protein Chemical Co., Ltd. makes] (50.3g, 0.2mol) and NaF[Kanto KagakuCo., Ltd. makes] (and 58.8g, 1.4mol), 60-80 ℃ next time stream reacted 8 hours.After reaction is finished,, obtain wherein all A by distilling the purified reaction product down at 50 ℃ 2General formula (III) phosphazene derivative for F.
Then, in 75mL THF, add wherein all A 2For general formula (III) phosphazene derivative of F (24.9g, 0.1mol), aniline (14g, 0.15mol) and potash (27.6g, 0.2mol), and 80 ℃ of reactions 10 hours down.Reaction is displayed it 1 day, then by removing by filter the potash of accessory substance potassium fluoride, saleratus, aniline salt and excessive adding after finishing.Gained filtrate fully dewatered and add lithium methoxide (5.7g, 0.15mol), and 45 ℃ of reactions 5 hours down.After reaction is finished, separate and purify, obtain wherein six A by the method for recrystallization 1In one be that NphLi, all the other five are the general formula of F (I) compound Z (19.7g, 0.06mol, productive rate: 60%).
When using the compound that the device analysis identical with synthetic embodiment 1 should synthetic embodiment, observe big mass number peak at 321,233 and 230 places.Six A wherein 1In one be 328 for NphLi, all the other five molecular weight for the general formula of F (I) compound, and the quality of the fragment lose 1 Li and 5 fluorine from this compound after is consistent with above-mentioned assay value, thereby judges that compound that this synthetic embodiment obtains is six A wherein 1In one be that NphLi, all the other five are the general formula of F (I) compound.
(the synthetic embodiment 4 of supporting electrolyte)
In 75mL THF, add wherein all A that obtain in the fluorination step of above-mentioned synthetic embodiment 3 2For general formula (III) phosphazene derivative of F (24.9g, 0.1mol), aniline (42g, 45mol) and potash (69g, 0.5mol), and 80 ℃ of reactions 8 hours down.Reaction is displayed it 1 day, then by removing by filter the potash of accessory substance potassium fluoride, saleratus, aniline salt and excessive adding after finishing.Gained filtrate fully dewatered and add lithium methoxide (19.0g, 0.5mol), and 45 ℃ of reactions 5 hours down.After reaction is finished, separate and purify, obtain wherein six A by the method for recrystallization 1In three be NphLi, its excess-three and be the general formula of F (I) compound Y (32.6g, 0.067mol, productive rate: 67%).
When using the compound that the device analysis identical with synthetic embodiment 1 should synthetic embodiment, observe big mass number peak at 465,388,290 and 192 places.Six A wherein 1In three be 486 for NphLi, its excess-three a molecular weight for the general formula of F (I) compound, and the fragment quality lose 3 Li or 1-3 NPhLi from this compound after is consistent with above-mentioned assay value, thereby judges that compound that this synthetic embodiment obtains is six A wherein 1In three be NphLi, its excess-three and be the general formula of F (I) compound.
(the synthetic embodiment 5 of supporting electrolyte)
In the 150mL acetonitrile, add wherein all A 2For general formula (VI) phosphazene derivative of Cl [Nippon Kagaku Kogyo Co., Ltd. makes] (54g, 0.2mol) and NaF[KantoKagaku Co., Ltd. makes] (and 58.8g, 1.4mol), 90 ℃ of following back flow reaction 10 hours.After reaction is finished,, obtain wherein all A by distilling the purified reaction product down at about 96 ℃ 2General formula (VI) phosphazene derivative for F.
Then, in 150mL THF, add wherein all A 2For general formula (VI) phosphazene derivative of F (37.4g, 0.2mol), aniline (28g, 0.3mol) and potash (27.6g, 0.2mol), and 60 ℃ of reactions 12 hours down.Reaction is displayed it 1 day after finishing, and then by removing by filter the potash of accessory substance potassium fluoride, saleratus, aniline salt and excessive adding, (11.4g 0.3mol) and at 60 ℃ reacted 5 hours down to add lithium methoxide then.After reaction is finished, separate and purify, obtain wherein five A by the method for recrystallization 1In one be that NphLi, all the other four are the general formula of F (II) compounds X (22.3g, 0.084mol, productive rate: 42%).
When using the compound that the device analysis identical with synthetic embodiment 1 should synthetic embodiment, observe big mass number peak at 259,190 and 168 places.Five A wherein 1In one be 226 for NphLi, all the other four molecular weight for the general formula of F (II) compound, and the fragment quality after this compound loses 1 Li, 1 NPhLi or 4 fluorine is consistent with above-mentioned assay value, thereby judges that compound that this synthetic embodiment obtains is five A wherein 1In one be that NphLi, all the other four are the general formula of F (II) compound.
(the synthetic embodiment 6 of supporting electrolyte)
In 150mL THF, add wherein all A that obtain in the fluorination step of above-mentioned synthetic embodiment 5 2For general formula (VI) phosphazene derivative of F (37.4g, 0.2mol), aniline (84g, 0.9mol) and potash (138g, 1.0mol), back flow reaction 16 hours.Reaction is displayed it 1 day after finishing, and then by removing by filter the potash of accessory substance potassium fluoride, saleratus, aniline salt and excessive adding, (34.2g 0.9mol), and reacted 5 hours under 60 ℃ to add lithium methoxide then.After reaction is finished, separate and purify, obtain wherein five A by the method for recrystallization 1In three be that NphLi, all the other two are the general formula of F (II) compound W (59.4g, 0.14mol, productive rate: 70%).
When using the compound that the device analysis identical with synthetic embodiment 1 should synthetic embodiment, observe big mass number peak at 403,326,228 and 130 places.Five A wherein 1In three be 424 for NphLi, all the other two molecular weight for the general formula of F (II) compound, and the fragment quality after this compound loses 3 Li or 1-3 NPhLi is consistent with above-mentioned assay value, thereby judges that compound that this synthetic embodiment obtains is five A wherein 1In three be that NphLi, all the other two are the general formula of F (II) compound.
＜nonaqueous electrolytic solution primary cell 〉
(embodiment 1)
Mix and kneading manganese dioxide [EMD by ratio (mass ratio) with 8: 1: 1, MitsuiMining Co., Ltd.] acetylene black and polytetrafluoroethylene (PTFE) preparation be anodal, applies the material of kneading with scraper, dry in hot gas (100-120 ℃), by the perforating press cutting of Φ 16mm.Anodal quality is 20mg.
By (thickness: 0.5mm) prepare negative pole with Φ 16mm punching, the nickel film is as collector electrode to the lithium paper tinsel.In addition, dissolve in propylene glycol carbonate (PC) and dimethoxy-ethane (DME) (volume ratio: in mixed solution PC/DME=50/50), make electrolyte by compound (supporting electrolyte) with the concentration of 0.25mol/L (M) with general formula (XXI).
Use cellulose dividing plate (Ltd. makes for TF4030, Nippon Kodo Kami-Kogyo Co.) as dividing plate, above-mentioned positive pole and negative pole are oppositely arranged by this dividing plate, inject electrolyte therein, seal then, make the lithium primary cell (nonaqueous electrolytic solution primary cell) of CR2016 type.
For the lithium primary cell of such acquisition, measure and be evaluated at the initial cells characteristic (voltage, internal resistance) under 25 ℃, measure and assess average discharge potential and discharge capacity under the room temperature then by following method.In addition, following appraisal procedure according to JIS K7201 is measured used electrolytical limited oxygen index in the battery.The results are shown in the table 1.
-assess average discharge potential-
When under the 0.2C condition, positive electrode being discharged, in the discharge curve of gained, keep the current potential in the flat form on the calculated curve, as average discharge potential.
Discharge capacity under the-assessment room temperature-
By in 25 ℃ atmospheric environment with the constant current (0.2C) of 1mA to battery discharge to 1.5V (lower voltage limit), measure the discharge capacity under the room temperature.
-measuring limit oxygen index-
Strengthen the SiO of 127mm * 12.7mm with the U-shaped aluminium foil 2Sheet material (quartz filter paper, incombustible) becomes self-supporting (self-supported) state, uses this SiO of 1.0mL electrolyte-impregnated then 2Sheet material prepares sample thus.Sample vertically is attached on the sample support parts, make its position and combustion column (internal diameter: 75mm, high: 450mm, the glass particle of filling diameter 4mm from the bottom equably be to thick 100 ± 5mm, and place a wire netting thereon) upper part is separated by and is not less than the distance of 100mm.Then, oxygen (being equal to or higher than JIS K1101) and nitrogen (be equal to or higher than JIS K1107 2 grades) are flow through combustion column, and in empty body, light sample (thermal source is 1 type, the No.1 of JIS K2240), with the check fired state.Total flow is 11.4L/min in the combustion column.Repeated experiments three times, average value measured.
Keep the value of the needed minimum oxygen concentration of substance combustion under the fc-specific test FC condition that limited oxygen index refers to define among the JIS K7201, represent with percent by volume.Limited oxygen index of the present invention be according to sample continuous burning 3 minutes or the longer time or light after continuous burning make burning length be no less than the required minimum oxygen flow of 50mm and this moment the minimum nitrogen throughput calculate.
Equation: limited oxygen index=[oxygen flow]/([oxygen flow]+[nitrogen flow]) * 100 (volume %)
(embodiment 2)
According to embodiment 1 in identical method prepare lithium primary cell, difference is compound that the compound with general formula (XXII) replaces general formula (XXI) as supporting electrolyte, and with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 1.
(conventional embodiment 1)
According to embodiment 1 in identical method prepare lithium primary cell, difference is by with LiCF 3SO 3Dissolve in propylene glycol carbonate (PC) and dimethoxy-ethane (DME) (volume ratio: prepare electrolyte in mixed solution PC/DME=50/50), and measure and assess various battery behaviors and limited oxygen index with the concentration of 0.75mol/L (M) with identical method.The results are shown in table 1.
(embodiment 3)
According to embodiment 1 in identical method prepare lithium primary cell, difference is that (wherein n is 3 and six R by the compound (supporting electrolyte) of general formula (XXI) is dissolved in the phosphazene derivative A of 10 volume % with the concentration of 0.25mol/L (M) 5In two be that ethyoxyl, all the other four are the general formula of fluorine (XI) ring phosphazene derivative, viscosity under 25 ℃: 1.2mPas (1.2cP)) with the propylene glycol carbonate (PC) of 90 volume % and dimethoxy-ethane (DME) (volume ratio: PC/DME=50/50) prepare electrolyte in the mixed solution of mixed solution, and with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 1.
(embodiment 4)
According to embodiment 3 in identical method prepare lithium primary cell, difference is that (wherein n is 4 and eight R with phosphazene derivative B in the preparation electrolyte 5In one be that ethyoxyl, all the other seven are the general formula of fluorine (XI) ring phosphazene derivative, 25 ℃ of viscosity down: 1.3mPas (1.3cP)) replace phosphazene derivative A, and with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 1.
(embodiment 5)
According to embodiment 3 in identical method prepare lithium primary cell, difference is compound that the compound with general formula (XXII) replaces general formula (XXI) as supporting electrolyte, and with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 1.(embodiment 6)
According to embodiment 4 in identical method prepare lithium primary cell, difference is compound that the compound with general formula (XXII) replaces general formula (XXI) as supporting electrolyte, and with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 1.
Table 1
Supporting electrolyte The phosphorus nitrence that comprises in the electrolyte Initial potential (V) Internal resistance (Ω) Average discharge potential (V) Discharge capacity under the room temperature (mAh/g) Limited oxygen index (volume %)
Conventional embodiment 1 LiCF 3SO 3 - 3.46 0.12 2.80 225 18.6
Embodiment 1 General formula (XXI) - 3.57 0.13 2.94 231 22.4
Embodiment 2 General formula (XXII) - 3.61 0.10 2.95 238 22.2
Embodiment 3 General formula (XXI) Phosphorus nitrence A 3.64 0.12 2.95 239 24.8
Embodiment 4 General formula (XXI) Phosphorus nitrence B 3.65 0.12 2.97 241 25.8
Embodiment 5 General formula (XXII) Phosphorus nitrence A 3.62 0.12 2.96 239 24.6
Embodiment 6 General formula (XXII) Phosphorus nitrence B 3.61 0.13 2.94 245 25.6
(embodiment 7-10)
According to embodiment 1 in identical method prepare lithium primary cell, difference is that replacing the compound of general formula (XXI) with each compound described in the table 2 is the concentration shown in the table 2 as supporting electrolyte and this supporting electrolyte concentration, and measures and assess various battery behaviors and limited oxygen index with identical method.The results are shown in table 2.
(embodiment 11-14)
According to embodiment 3 in identical method prepare lithium primary cell, difference is that replacing the compound of general formula (XXI) with each compound described in the table 2 is the concentration shown in the table 2 as supporting electrolyte and this supporting electrolyte concentration, and measures and assess various battery behaviors and limited oxygen index with identical method.The results are shown in table 2.
(embodiment 15-18)
According to embodiment 4 in identical method prepare lithium primary cell, difference is that replacing the compound of general formula (XXI) with each compound described in the table 2 is the concentration shown in the table 2 as supporting electrolyte and this supporting electrolyte concentration, and measures and assess various battery behaviors and limited oxygen index with identical method.The results are shown in table 2.
Table 2
Supporting electrolyte Supporting electrolyte concentration (mol/L) The phosphorus nitrence that comprises in the electrolyte Initial potential (V) Internal resistance (Ω) Average discharge potential (V) Discharge capacity under the room temperature (mAh/g) Limited oxygen index (volume %)
Conventional embodiment 1 LiCF 3SO 3 0.75 - 3.46 0.12 2.80 225 18.6
Embodiment 7 Compound Z 1 - 3.54 0.12 2.91 241 23.1
Embodiment 8 Compound Y 0.5 - 3.55 0.13 2.95 243 22.9
Embodiment 9 Compounds X 1 - 3.52 0.11 2.96 242 23.3
Embodiment 10 Compound W 0.5 - 3.57 0.13 2.96 246 22.6
Embodiment 11 Compound Z 1 Phosphorus nitrence A 3.61 0.12 2.95 248 25.7
Embodiment 12 Compound Y 0.5 Phosphorus nitrence A 3.59 0.11 2.94 241 25.1
Embodiment 13 Compounds X 1 Phosphorus nitrence A 3.58 0.12 2.95 242 25.3
Embodiment 14 Compound W 0.5 Phosphorus nitrence A 3.52 0.12 2.94 242 25.7
Embodiment 15 Compound Z 1 Phosphorus nitrence B 3.57 0.13 2.96 242 26.1
Embodiment 16 Compound Y 0.5 Phosphorus nitrence B 3.56 0.13 2.97 243 25.9
Embodiment 17 Compounds X 1 Phosphorus nitrence B 3.59 0.12 2.95 242 25.8
Embodiment 18 Compound W 0.5 Phosphorus nitrence B 3.61 0.11 2.96 245 26.0
＜nonaqueous electrolytic solution secondary battery 〉
(embodiment 19)
To 100 mass parts LiCoO 2[Nippon Kagaku Kogyo Co., Ltd. make] middle 10 mass parts acetylene blacks and the 10 mass parts polytetrafluoroethylene (PTFE)s of adding, and kneading in organic solvent (ethyl acetate of 50/50 volume % and ethanol mixed solvent), by the running roller roll-in, be prepared into the anodal sheet material of the thin layer shape of thick 100 μ m, wide 40mm.Then, sandwich between two anodal sheet materials that layer of surface has been coated with conductive adhesive and thickness is the aluminium foil (collector electrode) of 25 μ m, by thickness is the dividing plate (microporous membrane of 25 μ m, make by polypropylene) pile up the lithium metal foil that a layer thickness is 150 μ m thereon, cylindrical electrode is made in its coiling.Anodal length in the cylindrical electrode is about 260mm.
Dissolve in the mixed solution of 50 volume % diethyl carbonates (DEC) and 50 volume % ethylene carbonate esters (EC) with the concentration of 0.25mol/L (M) by compound (supporting electrolyte), make electrolyte general formula (XXI).This electrolyte is injected cylindrical electrode and seal, prepare the lithium secondary battery (nonaqueous electrolytic solution secondary battery) of AA size.
For the lithium secondary battery of such acquisition, measure and be evaluated at the initial cells characteristic (voltage, internal resistance) under 25 ℃, measure by following method then and assessment discharge-charging cycle performance.In addition, use the method identical to measure the limited oxygen index of used electrolyte in this battery with embodiment 1.The results are shown in table 3.
-assessment discharge-charging performance-
In 25 ℃ atmospheric environment, battery is repeated discharge-charging cycle 50 times under the condition of upper voltage limit: 4.3V, lower voltage limit: 3.0V, discharging current: 100mA and charging current: 50mA, measuring initial discharge-charging capacity and 50 circulations discharge-charging capacity afterwards.
(embodiment 20)
According to embodiment 19 in identical method prepare lithium secondary battery, difference is compound that the compound with general formula (XXII) replaces general formula (XXI) as supporting electrolyte, and with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 3.
(conventional embodiment 2)
According to embodiment 19 in identical method prepare lithium secondary battery, difference is by with LiBF 4Dissolve in the concentration of 0.75mol/L (M) in the mixed solution of 50 volume % diethyl carbonates (DEC) and 50 volume % ethylene carbonate esters (EC) and prepare electrolyte, and measure and assess various battery behaviors and limited oxygen index with identical method.The results are shown in table 3.
(embodiment 21)
According to embodiment 19 in identical method prepare lithium secondary battery, difference is that (wherein n is 3 and six R by the compound (supporting electrolyte) of general formula (XXI) is dissolved in the phosphazene derivative C of 10 volume % with the concentration of 0.25mol/L (M) 5In one be that ethyoxyl, all the other five are the general formula of fluorine (XI) ring phosphazene derivative, viscosity under 25 ℃: 1.2mPas (1.2cP)), prepare electrolyte in the mixed solution of the diethyl carbonate (DEC) of 45 volume % and 45 volume % ethylene carbonate esters (EC), and measure and assess various battery behaviors and limited oxygen index with identical method.The results are shown in table 3.
(embodiment 22)
According to embodiment 21 in identical method prepare lithium secondary battery, difference is that (wherein n is 3 and six R with phosphazene derivative D in preparation electrolyte 5In one be that positive propoxy, all the other five are the general formula of fluorine (XI) ring phosphazene derivative, 25 ℃ of viscosity down: 1.1mPas (1.1cP)) replace phosphazene derivative C, and with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 3.
(embodiment 23)
According to embodiment 21 in identical method prepare lithium secondary battery, difference is compound that the compound with general formula (XXII) replaces general formula (XXI) as supporting electrolyte, and with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 3.(embodiment 24)
According to embodiment 22 in identical method prepare lithium secondary battery, difference is compound that the compound with general formula (XXII) replaces general formula (XXI) as supporting electrolyte, and with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 3.
Table 3
Supporting electrolyte The phosphorus nitrence that comprises in the electrolyte Initial potential (V) Internal resistance (Ω) Average discharge potential (V) Initial discharge-charging capacity (mAh/g) Discharge-charging capacity (mAh/g) after 50 circulations Limited oxygen index (volume %)
Conventional embodiment 2 LiBF 4 - 2.86 0.12 4.1 143 130 19.0
Embodiment 19 General formula (XXI) - 2.84 0.13 4.1 143 141 21.8
Embodiment 20 General formula (XXII) - 2.82 0.12 4.1 144 141 21.4
Embodiment 21 General formula (XXI) Phosphorus nitrence C 2.84 0.12 4.1 144 143 24.8
Embodiment 22 General formula (XXI) Phosphorus nitrence D 2.84 0.11 4.1 144 143 25.0
Embodiment 23 General formula (XXII) Phosphorus nitrence C 2.86 0.12 4.1 144 142 24.6
Embodiment 24 General formula (XXII) Phosphorus nitrence D 2.84 0.11 4.1 144 143 24.8
(embodiment 25-28)
According to embodiment 19 in identical method prepare lithium secondary battery, difference is to replace the compound of general formula (XXI) to make supporting electrolyte and this supporting electrolyte concentration is the concentration shown in the table 4 with each compound described in the table 4, with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 4.
(embodiment 29-32)
According to embodiment 21 in identical method prepare lithium secondary battery, difference is to replace the compound of general formula (XXI) to make supporting electrolyte and this supporting electrolyte concentration is the concentration shown in the table 4 with each compound described in the table 4, with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 4.
(embodiment 33-36)
According to embodiment 22 in identical method prepare lithium secondary battery, difference is to replace the compound of general formula (XXI) to make supporting electrolyte and this supporting electrolyte concentration is the concentration shown in the table 4 with each compound described in the table 4, with identical method measurement with assess various battery behaviors and limited oxygen index.The results are shown in table 4.
Table 4
Supporting electrolyte Supporting electrolyte concentration (mol/L) The phosphorus nitrence that comprises in the electrolyte Initial potential (V) Internal resistance (Ω) Average discharge potential (V) Initial discharge-charging capacity (mAh/g) Discharge-charging capacity (mAh/g) after 50 circulations Limited oxygen index (volume %)
Conventional embodiment 2 LiBF 4 0.75 - 2.86 0.12 4.1 143 130 19.0
Embodiment 25 Compound Z 1 - 2.84 0.11 4.1 144 143 22.4
Embodiment 26 Compound Y 0.5 - 2.86 0.12 4.1 144 142 21.8
Embodiment 27 Compounds X 1 - 2.87 0.12 4.1 143 141 22.4
Embodiment 28 Compound W 0.5 - 2.88 0.13 4.1 145 141 21.6
Embodiment 29 Compound Z 1 Phosphorus nitrence C 2.89 0.13 4.1 143 139 24.9
Embodiment 30 Compound Y 0.5 Phosphorus nitrence C 2.91 0.12 4.1 145 140 25.1
Embodiment 31 Compounds X 1 Phosphorus nitrence C 2.91 0.13 4.1 144 141 25.1
Embodiment 32 Compound W 0.5 Phosphorus nitrence C 2.92 0.12 4.1 146 141 25.1
Embodiment 33 Compound Z 1 Phosphorus nitrence D 2.93 0.13 4.1 145 140 25.8
Embodiment 34 Compound Y 0.5 Phosphorus nitrence D 2.90 0.12 4.1 147 143 25.8
Embodiment 35 Compounds X 1 Phosphorus nitrence D 2.93 0.13 4.1 146 143 26.1
Embodiment 36 Compound W 0.5 Phosphorus nitrence D 2.93 0.13 4.1 145 142 26.1
Find out from these results, improved the limited oxygen index and the fail safe that has improved battery of electrolyte by adopting supporting electrolyte of the present invention.In addition, supporting electrolyte of the present invention can improve the conductivity of electrolyte as the ion source of lithium ion, thereby adopts the battery behavior of battery of this supporting electrolyte identical with the battery behavior of conventional embodiment battery.In addition, should also be understood that, improved the fail safe of battery more by adding the limited oxygen index that phosphazene derivative has further improved electrolyte to electrolyte.
＜polymer battery 〉
(embodiment 37)
[preparation polymer dielectric]
Mix 15g poly(ethylene oxide) [Ardrich manufacturings] (Mw=5000000-6000000) with the compound (supporting electrolyte) of 5mmol general formula (XXI) and add the 10mL acetonitrile, it is evenly mixed down and dissolving at 80 ℃, obtain poly(ethylene oxide) colloidal sol (compound that comprises poly(ethylene oxide) and general formula (XXI)).This colloidal sol to 40 of heating ℃ evaporation acetonitrile and dry under vacuum.Pass through then to immerse the mixed solution (DEC/EC=1/1 (volume ratio)) of 1mL diethyl carbonate (DEC) and ethylene carbonate ester (EC) with its swelling.Measure the limited oxygen index of polymer dielectric with the method that defines among the JIS K7201.The results are shown in table 5.
[preparation polymer battery]
To 100 mass parts LiCoO 2[Nippon Kagaku Kogyo Co., Ltd. make] middle 10 mass parts acetylene blacks and the 10 mass parts polytetrafluoroethylene (PTFE)s of adding, and integrate with organic solvent (ethyl acetate of 50/50 volume % and ethanol mixed solvent), by the running roller roll-in, be prepared into the anodal sheet material of the thin layer shape of thick 100 μ m, wide 40mm.In addition, be that the graphite sheet of 150 μ m is made negative pole with thickness.
Then, according to above-mentioned polymer dielectric preparation process in identical method prepare poly(ethylene oxide) colloidal sol, and this colloidal sol is applied on two surfaces of polyethylene separator with scraper, making its thickness is 150 μ m, evaporate acetonitrile then, prepare poly(ethylene oxide)-lithium gel electrolyte (xerogel).Be clipped between anodal sheet material and the negative electrode plate (graphite sheet) this gel and coiling, by the further swelling of the mixed solution (DEC/EC=1/1 (volume ratio)) that immerses diethyl carbonate (DEC) and ethylene carbonate ester (EC), prepare the polymer battery of AA size.The length of the positive pole in the battery is about 260mm.
For the battery of such acquisition, measure and be evaluated at the initial cells characteristic (voltage, internal resistance) under 25 ℃, measure and assess the effect of discharge-charging cycle performance, low temperature performance, high-temperature storage performance and inhibition dendrite deposition then by following method.The results are shown in table 5.-assessment discharge-charging cycle performance-
In 25 ℃ atmospheric environment, battery is being repeated discharge-charging cycle 50 times under the condition of upper voltage limit: 4.3V, lower voltage limit: 3.0V, discharging current: 100mA and charging current: 50mA.By with the comparison of initial discharge-charging capacity, calculate the ratio that capacity reduces after 50 circulations.Carry out identical measurement and assessment to amounting to three batteries, a mean value is provided, this value is the assessment to discharge-charging cycle performance.
-assessment cryogenic discharging characteristic (measuring the low temperature discharge capacity)-
Battery is in down charging and in low temperature (20 ℃) discharge down of room temperature (25 ℃), the discharge capacity this low temperature under and battery are discharged under 25 ℃-discharge capacity when charging compares, by the minimizing ratio of following equation calculating discharge capacity.Carry out identical measurement and assessment to amounting to three batteries, a mean value is provided, this value is the assessment to cryogenic discharging characteristic.
Equation: the minimizing ratio=100-of discharge capacity (low temperature discharge capacity/discharge capacity (25 ℃)) * 100%
-assessment high-temperature storage performance (flash-over characteristic after measurement and the assessment high-temperature test under the room temperature)-
After 10 days, measure and assess the flash-over characteristic (discharge capacity (mAh/g) etc.) under the room temperature (25 ℃) in storage under 80 ℃.Measuring and assessing in this flash-over characteristic, the internal resistance (Ω, 25 ℃, 1kHz impedance) when also measuring 50% depth of discharge (being discharged to 50% state of all told).
The effect of-assessment inhibition dendrite deposition-
After 25 ℃ of discharges that repeat down IC-charging 30 times, take battery apart, the inner surface of perusal positive pole and negative pole.The result does not have special survey to the lithium deposition, does not change.
(embodiment 38)
According to embodiment 37 in identical method prepare polymer dielectric and polymer battery, difference is to replace the compound of general formula (XXI) to make supporting electrolyte with the compound of general formula (XXII), and measures and assessment limited oxygen index and various battery behavior.In addition, observe according to the method identical and whether to exist dendrite deposition, result not to have special survey, do not change to the lithium deposition with embodiment 37.This results are shown in table 5.
(conventional embodiment 3)
According to embodiment 37 in identical method prepare polymer dielectric and polymer battery, difference is to use LiPF 6Replace the compound of general formula (XXI) to make supporting electrolyte, and measure and assessment limited oxygen index and various battery behavior.In addition, observe whether there is the dendrite deposition according to the method identical with embodiment 37, results verification has crystalline lithium (dendrite) growth in negative terminal surface.In addition, trickle irregular at anodal surface observation to what cause because of granular lithium deposition.These the results are shown in table 5.
(embodiment 39)
[preparation nonaqueous electrolytic solution]
(wherein n is 3 and six R to add 2.5mL phosphazene derivative A in the mixed solvent (DEC/EC=1/1 (volume ratio)) of diethyl carbonate (DEC) and ethylene carbonate ester (EC) 5In two be that ethyoxyl, all the other four are the general formula of fluorine (XI) ring phosphazene derivative compound, 25 ℃ of following viscosity: 1.2mPas (1.2cP)), prepare nonaqueous electrolytic solution thus.
[preparation polymer dielectric]
According to embodiment 37 in identical method prepare polymer dielectric, difference is to immerse the nonaqueous electrolytic solution of the above-mentioned preparation of 1mL, the mixed solvent (DEC/EC=1/1 (volume ratio)) that replaces diethyl carbonate (DEC) and ethylene carbonate ester (EC), and the limited oxygen index of measurement polymer dielectric.The results are shown in table 5.
[preparation polymer battery]
According to embodiment 37 in identical method prepare polymer battery, difference is to immerse the nonaqueous electrolytic solution and the swelling of above-mentioned preparation, the mixed solvent (DEC/EC=1/1 (volume ratio)) that replaces diethyl carbonate (DEC) and ethylene carbonate ester (EC), and measure and assess various battery behaviors.In addition, observe according to the method identical and whether to exist dendrite deposition, result not to have special survey, do not change to the lithium deposition with embodiment 37.These the results are shown in table 5.
(embodiment 40)
According to embodiment 37 in identical method prepare polymer dielectric and polymer battery, difference is that (wherein n is 3 and six R with phosphorus nitrence Compound C 5In one be that ethyoxyl, all the other five are the general formula of fluorine (XI) ring phosphazene derivative compound, 25 ℃ of following viscosity: 1.2mPas (1.2cP)) replace phosphorus nitrence compd A, and measure and assessment limited oxygen index and various battery behavior.In addition, observe according to the method identical and whether to exist dendrite deposition, result not to have special survey, do not change to the lithium deposition with embodiment 37.These the results are shown in table 5.
(embodiment 41)
According to embodiment 39 in identical method prepare polymer dielectric and polymer battery, difference is to replace the compound of general formula (XXI) to make supporting electrolyte with the compound of general formula (XXII), and measures and assessment limited oxygen index and various battery behavior.In addition, observe according to the method identical and whether to exist dendrite deposition, result not to have special survey, do not change to the lithium deposition with embodiment 37.These the results are shown in table 5.
(embodiment 42)
According to embodiment 40 in identical method prepare polymer dielectric and polymer battery, difference is to replace the compound of general formula (XXI) to make supporting electrolyte with the compound of general formula (XXII), and measures and assessment limited oxygen index and various battery behavior.In addition, observe according to the method identical and whether to exist dendrite deposition, result not to have special survey, do not change to the lithium deposition with embodiment 37.These the results are shown in table 5.
Table 5
Supporting electrolyte The phosphorus nitrence that comprises in the electrolyte Limited oxygen index (volume %) Initial potential (V) Initial internal resistance (Ω) Cycle performance Cryogenic discharging characteristic High-temperature storage characteristics The dendrite deposition
Discharge-charging capacity reduces ratio (%) Discharge capacity reduces ratio (%) Discharge capacity (mAh/g) 1kHz impedance (Ω)
Conventional embodiment 3 LiPF 6 - 17.4 3.02 0.12 12 68 78 122.1 Deposition
Embodiment 37 General formula (XXI) - 21.8 2.89 0.12 5 55 112 71.5 There is not deposition
Embodiment 38 General formula (XXII) - 21.4 2.87 0.12 5 53 106 73.2 There is not deposition
Embodiment 39 General formula (XXI) Phosphorus nitrence A 23.2 2.80 0.11 4 38 118 58.1 There is not deposition
Embodiment 40 General formula (XXI) Phosphorus nitrence C 24.1 2.79 0.10 3 32 121 55.8 There is not deposition
Embodiment 41 General formula (XXII) Phosphorus nitrence A 23.0 2.81 0.10 4 35 119 59.0 There is not deposition
Embodiment 42 General formula (XXII) Phosphorus nitrence C 23.9 2.79 0.09 3 31 120 55.1 There is not deposition
(embodiment 43-46)
According to embodiment 37 in identical method prepare polymer dielectric and polymer battery, difference is that the concentration that replaces the compound of general formula (XXI) to make supporting electrolyte and this supporting electrolyte with the compound described in the table 6 is the concentration shown in the table 6, measures and assessment limited oxygen index and various battery behavior.In addition, observe according to the method identical and whether to exist dendrite deposition, result not to have special survey, do not change to the lithium deposition with embodiment 37.This results are shown in table 6.
(embodiment 47-50)
According to embodiment 39 in identical method prepare polymer dielectric and polymer battery, difference is that the concentration that replaces the compound of general formula (XXI) to make supporting electrolyte and this supporting electrolyte with the compound described in the table 6 is the concentration shown in the table 6, measures and assessment limited oxygen index and various battery behavior.In addition, observe according to the method identical and whether to exist dendrite deposition, result not to have special survey, do not change to the lithium deposition with embodiment 37.This results are shown in table 6.
(embodiment 51-54)
According to embodiment 40 in identical method prepare polymer dielectric and polymer battery, difference is that the concentration that replaces the compound of general formula (XXI) to make supporting electrolyte and this supporting electrolyte with the compound described in the table 6 is the concentration shown in the table 6, measures and assessment limited oxygen index and various battery behavior.In addition, observe according to the method identical and whether to exist dendrite deposition, result not to have special survey, do not change to the lithium deposition with embodiment 37.These the results are shown in table 6.
Table 6
Supporting electrolyte The phosphorus nitrence that comprises in the electrolyte Limited oxygen index (volume %) Initial potential (V) Initial internal resistance (Ω) Cycle performance Cryogenic discharging characteristic High-temperature storage characteristics The dendrite deposition
Discharge-charging capacity reduces ratio (%) Discharge capacity reduces ratio (%) Discharge capacity (mAh/g) 1kHz impedance (Ω)
Conventional embodiment 3 LiPF 6 - 17.4 3.02 0.12 12 68 78 122.1 Deposition
Embodiment 43 Compound Z - 23.0 2.84 0.11 3 35 111 26.8 There is not deposition
Embodiment 44 Compound Y - 22.9 2.84 0.11 2 38 119 27.2 There is not deposition
Embodiment 45 Compounds X - 22.6 2.86 0.11 4 35 115 27.8 There is not deposition
Embodiment 46 Compound W - 22.0 2.85 0.11 3 26 121 22.0 There is not deposition
Embodiment 47 Compound Z Phosphorus nitrence A 24.6 2.87 0.12 3 26 121 22.0 There is not deposition
Embodiment 48 Compound Y Phosphorus nitrence A 24.9 2.85 0.11 4 24 120 22.2 There is not deposition
Embodiment 49 Compounds X Phosphorus nitrence A 24.9 2.83 0.11 4 27 123 20.0 There is not deposition
Embodiment 50 Compound W Phosphorus nitrence A 25.0 2.83 0.10 3 25 122 23.1 There is not deposition
Embodiment 51 Compound Z Phosphorus nitrence C 25.0 2.83 0.10 2 20 126 19.5 There is not deposition
Embodiment 52 Compound Y Phosphorus nitrence C 25.0 2.80 0.10 3 18 127 18.4 There is not deposition
Embodiment 53 Compounds X Phosphorus nitrence C 24.9 2.80 0.10 2 19 125 19.0 There is not deposition
Embodiment 54 Compound W Phosphorus nitrence C 25.2 2.76 0.09 2 18 128 18.6 There is not deposition
Find out from these results, improved the limited oxygen index of polymer dielectric, improved the fail safe of using this electrolytical polymer battery by the supporting electrolyte that adopts general formula (I) or compound (II) to constitute.In addition, because the supporting electrolyte that general formula (I) or compound (II) constitute is fully as the ion source of lithium ion, can improve the conductivity of polymer dielectric, the battery behavior that therefore should understand the polymer battery that adopts this supporting electrolyte is identical with the battery behavior of conventional embodiment polymer battery.In addition, also see, further improved electrolytical limited oxygen index, improved the fail safe of battery more by soaking into swelling with the organic solvent that adds phosphazene derivative.
Industrial applicibility
According to the present invention, a kind of supporting electrolyte can be provided, it can be used in nonaqueous electrolytic solution and polymer dielectric, suppresses the burning of nonaqueous electrolytic solution and polymer dielectric. In addition, by consisting of battery with nonaqueous electrolyte with this supporting electrolyte, can provide a kind of battery with nonaqueous electrolyte of high security. And, by in the electrolyte of this battery, adding phosphazene derivative and/or phosphazene derivative isomers, can provide the battery with nonaqueous electrolyte with suitable high security.
By in the electrolyte of polymer battery, using above-mentioned supporting electrolyte, can provide a kind of anti-flammability outstanding, can not cause ignition danger and high security, can not cause electrolyte leakage, can miniaturization and thinning and hold easy-to-assemble polymer battery at various device. And, more guarantee to reduce the dangerous polymer battery with improving security of ignition by in polymer dielectric, comprising phosphazene derivative and/or phosphazene derivative isomers, can providing.

Claims (26)

1. supporting electrolyte for cell, it comprises by the following general formula (I) or (II) compound of expression:
At general formula (I) with (II), A 1Be NRLi or F independently, and at least one A 1Be NRLi, R is the monovalence substituting group.
2. according to the supporting electrolyte for cell of claim 1, its formula of (I) and (II) in R be phenyl.
3. method for preparing supporting electrolyte for cell, it comprises the following steps:
(i) with the phosphazene derivative of following general formula (III) expression and the primary amine reaction of following general formula (IV) expression, prepare the phosphazene derivative of following general formula (V) expression; With
(ii) in the phosphazene derivative of general formula (V), add pure lithium salts, the compound of preparation following formula (I) expression:
Figure C038171860002C2
A wherein 2Be F or Cl,
R-NH 2 .....(IV)
Wherein R is the monovalence substituting group,
A wherein 3Be NHR or F independently, and at least one A 3Be NHR, R is the monovalence substituting group,
A wherein 1Be NRLi or F independently, and at least one A 1Be NRLi, R is the monovalence substituting group.
4. according to the method for preparing supporting electrolyte for cell of claim 3, the primary amine of its formula of (IV) is an aniline.
5. method for preparing supporting electrolyte for cell, it comprises the following steps:
(i) with the phosphazene derivative of following general formula (VI) expression and the primary amine reaction of following general formula (IV) expression, prepare the phosphazene derivative of following general formula (VII) expression; With
(ii) in the phosphazene derivative of general formula (VII), add pure lithium salts, preparation following formula (II) expression compound:
A wherein 2Be F or Cl,
R-NH 2 .....(IV)
Wherein R is the monovalence substituting group,
A wherein 3Be NHR or F independently, and at least one A 3Be NHR, R is the monovalence substituting group,
A wherein 1Be NRLi or F independently, and at least one A 1Be NRLi, R is the monovalence substituting group.
6. according to the method for preparing supporting electrolyte for cell of claim 5, the primary amine of its formula of (IV) is an aniline.
7. a battery with nonaqueous electrolyte comprises positive pole, negative pole and nonaqueous electrolytic solution, and wherein nonaqueous electrolytic solution comprises the supporting electrolyte described in proton-inert organic solvent and the claim 1.
8. according to the battery with nonaqueous electrolyte of claim 7, wherein in proton-inert organic solvent, add phosphazene derivative or phosphazene derivative isomers.
9. battery with nonaqueous electrolyte according to Claim 8, wherein the viscosity of phosphazene derivative under 25 ℃ is no more than 300mPas (300cP), and by following general formula (VIII) or (IX) expression:
R wherein 1, R 2And R 3Be monovalence substituting group or halogen independently, X 1For comprising the substituting group of at least a element that is selected from carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulphur, selenium, tellurium and polonium, Y 1, Y 2And Y 3Be divalent linker, diad or singly-bound independently,
(NPR 4 2) n .....(IX)
R wherein 4Be monovalence substituting group or halogen independently, n is 3-15.
10. according to the battery with nonaqueous electrolyte of claim 9, the phosphazene derivative of its formula of (IX) is represented by following general formula (X):
(NPF 2) n .....(X)
Wherein n is 3-13.
11. according to the battery with nonaqueous electrolyte of claim 9, the phosphazene derivative of its formula of (IX) is represented by following general formula (XI):
(NPR 5 2) n .....(XI)
R wherein 5Be monovalence substituting group or fluorine independently, and all R 5In at least one be fluorine-containing monovalence substituting group or fluorine, n is 3-8, but not all R 5It all is fluorine.
12. battery with nonaqueous electrolyte according to Claim 8, wherein phosphazene derivative is solid down at 25 ℃, and is represented by following general formula (XII):
(NPR 6 2) n .....(XII)
R wherein 6Be monovalence substituting group or halogen independently, n is 3-6.
13. battery with nonaqueous electrolyte according to Claim 8, wherein the isomers of phosphazene derivative is represented by following general formula (XIII), and is the isomers of the phosphazene derivative of following general formula (XIV) expression:
At general formula (XIII) with (XIV), R 7, R 8And R 9Be monovalence substituting group or halogen independently, X 2For comprising the substituting group of at least a element that is selected from carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulphur, selenium, tellurium and polonium, Y 7And Y 8Be divalent linker, diad or singly-bound independently.
14. a polymer battery comprises positive pole, negative pole, comprises the electrolyte and the polymer of the described supporting electrolyte of claim 1.
15. according to the polymer battery of claim 14, wherein polymer is at least a in poly(ethylene oxide), polyacrylate and the PPOX.
16. according to the polymer battery of claim 14, wherein the weight average molecular weight of polymer is not less than 100000.
17. according to the polymer battery of claim 14, wherein the weight average molecular weight of polymer is not less than 5000000.
18. according to the polymer battery of claim 14, wherein the total amount of relative polymer of the amount of polymer and supporting electrolyte is 80～95 quality %.
19. according to the polymer battery of claim 14, wherein electrolyte further contains the isomers of phosphazene derivative and/or phosphazene derivative.
20. according to the polymer battery of claim 19, wherein the viscosity of phosphazene derivative under 25 ℃ is no more than 300mPas (300cP), and represents by following general formula (VIII) or (IX):
R wherein 1, R 2And R 3Be monovalence substituting group or halogen independently, X 1For comprising the substituting group of at least a element that is selected from carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulphur, selenium, tellurium and polonium, Y 1, Y 2And Y 3Be divalent linker, diad or singly-bound independently,
(NPR 4 2) n .....(IX)
R wherein 4Be monovalence substituting group or halogen independently, n is 3-15.
21. according to the polymer battery of claim 20, the phosphazene derivative of its formula of (IX) is represented by following general formula (X):
(NPF 2) n .....(X)
Wherein n is 3-13.
22. according to the polymer battery of claim 20, the phosphazene derivative of its formula of (IX) is represented by following general formula (XI):
(NPR 5 2) n .....(XI)
R wherein 5Be monovalence substituting group or fluorine independently, and all R 5In at least one be fluorine-containing monovalence substituting group or fluorine, n is 3-8, but not all R 5It all is fluorine.
23. according to the polymer battery of claim 19, wherein phosphazene derivative is solid down at 25 ℃, and is represented by following general formula (XII):
(NPR 6 2) n .....(XII)
R wherein 6Be monovalence substituting group or halogen independently, n is 3-6.
24. according to the polymer battery of claim 19, wherein the isomers of phosphazene derivative is represented by following general formula (XIII), and is the isomers of the phosphazene derivative of following general formula (XIV) expression:
At general formula (XIII) with (XIV), R 7, R 8And R 9Be monovalence substituting group or halogen independently, X 2For comprising the substituting group of at least a element that is selected from carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulphur, selenium, tellurium and polonium, Y 7And Y 8Be divalent linker, diad or singly-bound independently.
25. according to the polymer battery of claim 19, wherein the total content of phosphazene derivative and phosphazene derivative isomers is at least 0.5 quality % in the electrolyte.
26. according to the polymer battery of claim 25, wherein the total content of phosphazene derivative and phosphazene derivative isomers is at least 2.5 quality % in the electrolyte.
CNB038171864A 2002-06-19 2003-06-10 Supporting electrolyte for cell and method for production thereof, and cell Expired - Fee Related CN1300880C (en)

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